KR20060092241A - Ink for inkjet, ink set for inkjet, and inkjet recording method - Google Patents

Abstract

a dye; and water and/or a water- miscible organic solvent, wherein the dye comprises a dye compound having at least one heterocyclic structure, and the ink further comprises, as an additive, at least one compound capable of chemically interacting with the dye compound.

Description

Ink jet ink, ink jet ink set and ink jet recording method {INK FOR INKJET, INK SET FOR INKJET, AND INKJET RECORDING METHOD}

The present invention relates to an ink jet ink, an ink jet ink set, and an ink jet recording method.

With the recent popularization of computers, inkjet printers have been used for printing papers, films, fabrics and the like not only for office work but also for home use.

The ink jet recording method uses a piezoelectric element to apply pressure to the ink droplets to eject the ink droplets, thermally bubbles the ink to eject the droplets, uses ultrasonic waves, and absorbs the ink droplets by electrostatic force. The method of discharge is listed. As such an ink jet recording ink composition, an aqueous ink, an oil ink and a solid (melt) ink can be used. Among them, aqueous inks are mainly used because of their productivity, handleability, odorlessness and safety.

The colorants used in such inkjet recording inks are excellent in the following requirements: solubility in solvents; High concentration recording is possible; The color is good; Fastness to light, heat, air, water and chemicals; Good fixability to the water phase material with little bleed out; The storage stability of the ink is good; No toxicity; High purity; Inexpensive and easy to obtain must be satisfied. However, it is very difficult to obtain a colorant that satisfies all these requirements to a high level.

Various dyes and pigments have already been proposed for inkjet use and are currently used. However, at present, no coloring agent satisfying all of the above requirements is known. Dyestuffs and pigments, which are well known in the art, such as those listed on the C.I. list, could not satisfy all of the colors and fastnesses required for inkjet inks.

As dyes with improved fastness, azo dyes derived from aromatic amines and 5-membered heterocyclic amines are proposed in Japanese Patent Application Laid-open No. 55-161856. However, these dyes have a problem in that the colors of the yellow and cyan regions are not preferable, so that the color reproducibility is poor.

Japanese Patent Laid-Open Nos. 61-36362 and 2-212566 disclose inkjet recording inks capable of satisfying two requirements of color and light fastness. However, when the dyes used in these patent publications are used in water-soluble inks, they are insufficient in terms of solubility in water. In addition, when the dyes disclosed in these patent publications are used in waterjet inks for inkjet, there is a problem in terms of their wet heat fastness.

In order to solve these problems, PCT Patent Application Laid-open No. Hei 11-504958 discloses a compound and an ink composition. Further, an inkjet recording ink containing a pyrazolylaniline azo dye for improving the color and light fastness of the ink is described in Japanese Patent Laid-Open No. 2003-231850. However, these inkjet recording inks were insufficient in terms of color reproducibility and color fastness of the output image.

In addition, many cases have been found in which the preservation of the image is seriously deteriorated when the image is printed on an inkjet-only glossy paper at the photographic level and the printed matter is left in the room. The inventors assume that this phenomenon is caused by any oxidizing gas in the air such as ozone. When the printed matter is stored in a glass frame or the like in order to prevent exposure to the air flow, the above phenomenon hardly appears, but the conditions of use of the printed matter are limited.

This phenomenon is very prominent in photographic inkjet glossy paper, which is a serious problem with the current inkjet recording method, which is one of the important features of forming image quality at photographic quality.

Up to now, the inventors of the present invention have studied various dyes of good color and good fastness, and have developed them as preferred colorants for inkjet recording. However, it has been found that sufficient fastness cannot be obtained by using water-soluble dyes alone.

In addition, the present inventors further examined the dye-containing aqueous inkjet ink and found that, in the weather resistance test of gray continuous gradation images and portrait photographs, there was a problem that the yellow portion of low concentration rapidly faded and the color balance of the image was broken. It was.

On the other hand, when the solvent remaining in the ink is insufficiently removed, it causes a problem that the inkjet print density decreases during storage (for example, the yellow portion may look faded or the black portion may change). In particular, it is important to suppress the concentration decrease at high temperatures and high humidity.

In view of the above problems, it is an object of the present invention to provide an ink jet ink and an ink set having good color and image fastness, and to provide an ink jet recording method.

The above object of the present invention is achieved by the following ink jet ink and ink set and the following ink jet recording method.

<1st aspect of this invention>

1) An inkjet ink containing a dye and water and / or a water miscible organic solvent, wherein the dye contains a dye compound having at least one heterocyclic structure, and the ink chemically interacts with the dye compound as an additive. An inkjet ink, characterized by containing at least one compound to be added.

2) The ink according to 1), wherein the dye compound has two aromatic heterocycles bonded to each other through an azo bond.

3) The ink according to 1) or 2), wherein the dye compound has a metal chelated aromatic heterocyclic structure.

4) The ink according to any one of 1) to 3), wherein the additive is a hydrogen bond compound.

5) lambda max in the visible absorption spectrum of the diluted aqueous solution according to any one of 1) to 4), wherein the additive is a mixture of a dye having a heterocyclic structure in a molar ratio of 1: 1 and has a maximum concentration of 1 mmol / L. The ink is shifted to 5 nm or more compared with the case where the said additive is not contained.

6) The ink according to any one of 1) to 5), wherein the additive has a cyclic amide structure, and the dye compound has a nitrogen-containing six-membered aromatic heterocycle.

7) The ink according to any one of 1) to 6), wherein the additive is a compound having a partial structure of the following general formula (A).

Wherein X represents an oxygen atom, a sulfur atom or N-R (R represents a hydrogen atom or an alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group or heterocyclic group); Z represents the atomic group which forms a 5-8 membered ring.

8) An ink set comprising at least one ink according to any one of 1) to 7).

9) An inkjet recording method comprising recording an image with an inkjet printer using one of the ink or ink set according to any one of 1) to 8).

<2nd aspect of this invention>

10) one or more yellow inks containing an aqueous medium and a yellow dye dispersed or dissolved in the aqueous medium; And a black ink containing at least one yellow dye, wherein the dye has an oxidation potential of more than 1.0 V (vs SCE); λ max is in the range of 390 nm to 470 nm; An ink set, wherein the absorbance ratio I (λ max +70 nm) / I (λ max) is at most 0.4, wherein I (λ max) is an absorbance of λ max, and I (λ max +70 nm) is an absorbance of λ max +70 nm. In the present invention, λ max of the ink means a wavelength showing the maximum absorbance when the ink is diluted with water so as to have a maximum absorption concentration within a range of 1 to 2 and measured with a spectrophotometer.

11) The ink set according to 10), wherein the absorbance ratio I (λ max +70 nm) / I (λ max) of the yellow dye is at most 0.2.

12) The ink set according to 10) or 11), wherein the yellow dye is a compound of the following general formula (1).

(A-N = N-B) n-L (1)

Wherein A and B each independently represent a heterocyclic group which is substituted as necessary; n is 1 or 2; L represents a hydrogen atom or a substituent bonded to any predetermined position of A or B.

13) The method of any one of 10) to 12), wherein the accelerated fading rate constant of the yellow ink is smaller than that of the black ink, and the accelerated fading rate constant is the following method: printing the ink to be analyzed on the reflection medium, and reflecting the The concentration D _B was measured with a status A filter; In the yellow region, one point of the sample having a reflection density (D _B ) of 0.90 to 1.10 is defined as the initial concentration of the ink, and the printed sample is forcibly faded by using an ozone fading tester that always generates 5 ppm of ozone. ; An ink set, characterized in that it is determined by a method of measuring the time at which the reflection density of the discolored sample is reduced to 80% of the initial concentration of the original sample, and inducing the accelerated fading rate constant of the ink therefrom.

14) The ink set according to any one of 10) to 13), wherein the concentration of the water-soluble organic solvent in the yellow ink is lower than that of the black ink.

15) The solvent according to any one of 10) to 14), wherein the total concentration of the solvent in the yellow ink is lower than that in the black ink, and the total concentration of the solvent is a glycol organic solvent, a glycol alkyl ether organic solvent, and an amide organic solvent. Ink set, characterized in that determined by summing the concentration of any two or more solvents selected from.

<3rd aspect of this invention>

16) An inkjet color recording method comprising recording an image on an aqueous material having an aqueous layer on a support using an ink composition containing at least one of a yellow azo dye and a black azo dye, and a water miscible organic solvent. And the absolute value of the image concentration change at the point where the reflection density in the? Max region of the recorded image is 1.5 is at most 20%.

17) The image according to 16), wherein an image having a reflection concentration of 1.5 in the λ max region is printed, and the change in density is represented by the following general formula (where Da represents the initial concentration of the image region, and Db is 80 ° C. and 15% RH The density after 7 days in the atmosphere).

Change in concentration (%) = (Db-Da) / Da × 100

18) The inkjet color recording method according to 16) or 17), wherein the dye is a yellow dye of the following general formula (1).

(A-N = N-B) n-L (1)

Wherein A and B each independently represent a heterocyclic group which is substituted as necessary; L represents a hydrogen atom, a chemical bond or a divalent linking group; n is 1 or 2; Provided that when n is 1, L is a hydrogen atom, both A and B are monovalent heterocyclic groups; when n is 2, L is a chemical bond or a divalent linking group, and one of A and B is a monovalent complex; Ventilation, and the other is a divalent heterocyclic group; When n is 2, two A may be same or different, and two B may be same or different.

It is preferable that a heterocyclic ring is a 5-membered or 6-membered heterocycle. It may have a monocyclic structure or a polycyclic structure in which two or more rings are condensed with each other; Or an aromatic hetero ring or a non-aromatic hetero ring may be sufficient. Preferably, heteroatoms constituting the heterocycle include N, O and S atoms. More preferably n is 2.

When L is a hydrogen atom, L may be bonded to any predetermined position of A or B. When L is a chemical bond or a divalent linking group, L may be bonded to any predetermined position of A or B, but is preferably to the cyclic carbon atom or hetero atom (preferably nitrogen atom) of heterocyclic group A or B. It is preferable to combine.

19) The inkjet color recording method according to any one of 16) to 18), wherein the ink composition further contains a surfactant, and the surfactant is a betaine-based surfactant.

20) The inkjet color recording method according to 19), wherein the betaine surfactant is represented by the following general formula (6).

(R) p-N- [L- (COOM) q] r (6)

Wherein R represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; L represents a divalent linking group; M represents a hydrogen atom, an alkali metal atom, an ammonium group, a protonated organic amine or a nitrogen-containing heterocyclic group, or a quaternary ammonium ion group, and when it is a counter ion for an ammonium ion having N atoms in the above formula, it does not exist as a cation. Not a group; q represents an integer of 1 or more; r represents an integer of 1 to 4; p represents an integer of 0 to 4; p + r is 3 or 4; when p + r is 4, the N atom in the formula is a protonated ammonium atom (= N ⁺ =); when q is 2 or more, COOM may be the same or different; when r is 2 or more, (L- (COOM) q) may be the same or different; When p is 2 or more, R may be same or different.

21) The ink composition according to any one of 16) to 20), wherein at least one of triethylene glycol monobutyl ether, diethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, and dipropylene glycol monomethyl ether is mixed. An inkjet color recording method characterized by containing as a chemical conversion organic solvent.

22) The inkjet color recording method according to any one of 16) to 21), wherein the dye has an oxidation potential that is greater than 1.0 V (vs SCE).

23) The inkjet color recording method according to any one of 16) to 22), wherein the aqueous layer contains white inorganic pigment particles.

<1st aspect of this invention>

This invention is demonstrated in detail below.

The ink jet ink of the present invention (sometimes referred to simply as "ink") contains a compound having a heterocyclic structure as a dye, and contains a compound capable of interacting with the dye molecule.

The dye having a heterocyclic structure used in the present invention is classified into the following three forms.

The first group includes dyes having aromatic heterocycles at the color development sites. Examples of this type of dye include azo dyes, azomethine dyes, indanil dyes, triarylmethane dyes, cyanine dyes, merocyanine dyes, oxonol dyes, anthraquinone dye derivatives, anthrapyridone dyes and aromatic heterochromic compounds at the coloring site. There are others with rings. The chromophoric sites shown here represent structural sites that participate in color formation in the backbone of the dye. Structural sites are substructures of the dye that, when added to or removed from the dye, significantly change the absorption region of the dye. In principle, the site consists of a conjugation structure that governs the π-electronic structure or the absorption properties of the dye. For example, when the site is removed, the main absorption of the dye may change from cyan to magenta, or the dye may become completely colorless.

The second group includes chelate dyes having aromatic heterocycles as partial structures. Examples include phthalocyanine dyes, azochelate dyes, and the like.

The third group includes dyes having an aromatic heterocycle in a portion other than the color development portion.

For example, the dye has a linking group which introduces a solubilizing group, or a linking group where two or more dye molecules are connected to each other to form a "bis-type" or "tris-type" compound.

Among them, those preferably used in the present invention are azo dyes, azomethine dyes, anthripyridone dyes and phthalocyanine dyes having aromatic heterocycles at the coloring sites thereof, as well as bis type azo dyes having aromatic heterocycles at the linking groups thereof. More preferred are azo dyes having an aromatic heterocycle in the color development site.

Among them, particularly preferably used in the present invention is a dye having two aromatic heterocycles bonded to each other through an azo bond, and a dye having a metal chelated aromatic heterocyclic structure (i.e., forming a chelate structure with a metal). Dye having an aromatic heterocycle).

Preferred dyes used in the present invention can be represented by the following general formula.

(A-N = N-B) n-L (1)

As the dye of the general formula (1), a yellow dye is preferable.

As the dye of the general formula (2), cyan dye is preferable.

As dye of General formula (3), magenta dye is preferable.

As the dye of the general formula (4), a black dye is preferable.

In General formula (1), A and B respectively independently represent the heterocyclic group substituted as needed. The heterocycle is preferably a 5- or 6-membered heterocycle. It may have a monocyclic structure or a polycyclic structure in which two or more rings are condensed with each other; Or an aromatic hetero ring or a non-aromatic hetero ring may be sufficient. Preferably, heteroatoms constituting the heterocycle include N, O and S atoms. n represents an integer selected from 1 or 2; L represents a substituent bonded to any predetermined position of A or B. when n is 1, L is a hydrogen atom or a monovalent substituent; When n is 2, L is a chemical bond or a divalent linking group.

In formula (2), X ₂₁ , X ₂₂ , X ₂₃ and X ₂₄ are each independently -SO-Z ₂ , -SO ₂ -Z ₂ , -SO ₂ NR ₂₁ R ₂₂ , a sulfo group, -CONR ₂₁ R ₂₂ or -COOR ₂₁ is represented.

Z ₂ independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. R ₂₁ and R ₂₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group. A substituted heterocyclic group is shown. Y ₂₁ , Y ₂₂ , Y ₂₃ and Y ₂₄ each independently represent a monovalent substituent.

a ₂₁ to a ₂₄ and b ₂₁ to b ₂₄ represent the number of substituents of X ₂₁ to X ₂₄ and Y ₂₁ to Y ₂₄ , respectively. a ₂₁ to a ₂₄ each independently represent a number of 0 to 4, but all of them are not 0 at the same time. b ₂₁ ~ b ₂₄ independently represent a number of 0-4 respectively. When a ₂₁ to a ₂₄ and b ₂₁ to b ₂₄ are two or more numbers, a plurality of X ₂₁ to X ₂₄ and Y ₂₁ to Y ₂₄ may be the same or different. M represents a hydrogen atom, a metal atom or an oxide, hydroxide or halide thereof.

In the formula (3), A ₃₁ is a heterocyclic diazo component A ₃₁ -N ₂ 5- - represents a moiety of.

B ₃₁ and B ₃₂ each represent = CR ₃₁ -or -CR ₃₂ =, or one of them is a nitrogen atom, and the other is = CR ₃₁ -or -CR ₃₂ =. B ₃₅ and B ₃₆ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl or arylsulfonyl group, or a sulfamoyl group, and The group may have a substituent.

G ₃ , R ₃₁ and R ₃₂ are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, or an acyl group , Hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (arylamino group, heterocyclic amino group included ), Acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkyl or arylthio group, alkyl or arylsulfonyl group , Heterocyclic sulfonyl group, alkyl or arylsulfinyl group, heterocyclic sulfinyl group, sulfamoyl group, sulfo group, or heterocyclic thio group; Each group may have a substituent.

R ₃₁ and R ₃₂ or R ₃₅ and R ₃₆ may be bonded to each other to form a 5- or 6-membered ring.

In formula (4), A ₄₁ , B _41, and C ₄₁ each independently represent an aromatic or heterocyclic group which is substituted as necessary; A ₄₁ and C ₄₁ are divalent groups, and B ₄₁ is a divalent group. m is 1 or 2; n is an integer of 0 or more. At least one of A ₄₁ , B ₄₁ and C ₄₁ is a heterocyclic group.

As the dye of the general formula (2), those represented by the following general formula (5) are preferable.

In the formula _{(5), X 51 ~ X} 54, Y 51 ~ Y 58 and M ₁ respectively have the same meaning as _{X 21 ~ X 24, Y 21} ~ Y 24 and M in the formula (2). a ₅₁ to a ₅₄ each independently represent an integer of 1 or 2;

Preferably, the dye used in the present invention has an oxidation potential (Eox) of at least 1.00 V (vs SCE). More preferably, the dye is above 1.00 V (vs SCE), more preferably above 1.10 V (vs SCE), particularly preferably above 1.20 V (vs SCE), most preferably 1.25 V (vs SCE). Has an oxidation potential in excess of.

In the measurement of the oxidation potential, various methods, such as the cyclic voltammetry (CV), the rotating ring disc electrode method, or the comb-tooth type electrode method, can be used. The measurement of the said oxidation potential is demonstrated concretely. The sample to be analyzed is dissolved in a solvent such as dimethylformamide or acetonitrile containing a supporting electrolyte such as sodium perchlorate or tetrapropylammonium perchlorate to a concentration of 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol / dm ⁻³ , The oxidation potential value vs. SCE (standard saturated calomel electrode) is measured according to the method described above. The supporting electrolyte and solvent used may be appropriately selected depending on the oxidation potential and solubility of the test sample. Examples of supported electrolytes and solvents that can be used herein are described in FUJISHIMA, Akira et al., Electrochemical Measurement Methods (1984, published by Gihodo), pp. 101-118.

The oxidation potential value may be off by about 10 millivolts due to the influence of the interpotential potential or the resistance of the sample solution, but may be corrected with a reference sample (for example, hydroquinone). In this way, the reproducibility of the potential value measured as described above is confirmed.

In the present invention, the oxidation potential of the dye is N, N-dimethylformamide containing 0.1 mol · dm ⁻³ of tetrapropylammonium perchlorate as a supporting electrolyte (wherein the concentration of the dye is 1 × 10 ⁻³ mol · dm ⁻³ SCE (standard saturated calomel electrode) is used as the reference electrode, graphite electrode is used as the electrode, and platinum electrode is used as the counter electrode. Some water-soluble dyes may be difficult to dissolve directly in N, N-dimethylformamide. In this case, the dye is dissolved in the smallest possible amount of water and then diluted with N, N-dimethylformamide to reduce the water content of the resulting dye solution to 2% or less.

Preferred examples of the dyes used in the present invention are Japanese Patent Laid-Open Nos. 2002-309115, 2002-309116, 2002-371079, 2002-371214, 2002-322151, 2003-64275, 2003 -49100, 2002-302623, 2002-294097, 2002-285050, 2002-275386, 2002-256167, 2002-327132, 2002-309118, 2003-3086 Publications 2003-3109, 2003-3099, 2003-12966, 2003-64287, 2003-119415, 2003-12952, 2004-91509, 2004-91528 And 2004-124017, and Japanese Patent Application No. 2002-333603.

The inkjet ink of the present invention contains 0.01 to 50% by weight, preferably 0.1 to 20% by weight, more preferably 0.5 to 15% by weight of the dye described above.

The present invention is characterized by adding an additive which can interact with the dye to the ink.

In the present invention, the interaction with the dye means chemical interaction with the dye. Chemical interactions shown here include coulomb interactions, CH-π interactions, van der Waals forces, hydrogen bonds, etc., as in NISHIO, Yukihiro's Introduction to intermolecular Force for Organic Chemistry (Kodan-sha Scientific, 2000). . In the present invention, compounds that can interact with the dye through hydrogen bonding are preferred.

Examples of the hydrogen bonding group include hydroxyl group, thi group, carbonyl group, carboxyl group, urethane group, ureido group, amido group, sulfonamido group, acylamino group, imido group, hydroxylamino group, amino group, amidino group and guanidino group. In this invention, the group which can form a hydrogen bond through a nitrogen atom is preferable, For example, an amido group, a urethane group, a ureido group, a sulfone amido group, an acylamino group, and an imido group are mentioned.

Among the above-mentioned compounds, those which are more preferably used in the present invention are those having amido bonds or sulfonamido bonds. Especially preferred are compounds having a structure in which a plurality of amido groups are continuously present.

Examples of compounds of this type include bioassociated materials such as amino acid derivatives.

Examples include glycine, glycylglycine, glycylglyciglycine, allantoin, glutamine, biuret, phenylglycine, taurine, lysine.

In the present invention, not only the compound itself but also a derivative in which a substituent is partially introduced may be used in the same manner.

Substitutable substituents include alkyl groups (preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n -Octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl), alkenyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 carbon atoms) To 8, such as vinyl, allyl, 2-butenyl, 3-pentenyl), an alkynyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 12, still more preferably 2 to 8, For example propargyl, 3-pentynyl, aryl groups (preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, still more preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, Naphthyl), amino group (preferably 0 to 20 carbon atoms, more preferably 0 to 12 carbon atoms, still more preferably 0 to 6 carbon atoms, such as amino and methyl Mino, dimethylamino, diethylamino, diphenylamino, dibenzylamino), an alkoxy group (preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 8 carbon atoms, Methoxy, ethoxy, butoxy), aryloxy group (preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, still more preferably 6 to 12 carbon atoms, such as phenyloxy, 2- Naphthyloxy), an acyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl), Alkoxycarbonyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl group (preferably Is 7-20 carbon atoms, More preferably, it is 7-16 carbon atoms, More preferably, Is 7 to 10 carbon atoms, such as phenyloxycarbonyl) and acyloxy group (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 10 carbon atoms, such as acetoxy , Benzoyloxy), acylamino group (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 10 carbon atoms, such as acetylamino, benzoylamino), alkoxycarbonylamino group ( Preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, more preferably 2 to 12 carbon atoms, such as methoxycarbonylamino, aryloxycarbonylamino group (preferably 7 to 20 carbon atoms) Dogs, more preferably 7 to 16 carbon atoms, still more preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino, and sulfonylamino groups (preferably 1 to 20 carbon atoms, more preferably 1 to 20 carbon atoms). 16, more preferably carbon 1-12, such as methanesulfonylamino, benzenesulfonylamino) sulfamoyl group (preferably 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, still more preferably 0 to 12 carbon atoms, For example sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, carbamoyl groups (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, For example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl), alkylthio groups (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably carbon atoms) 1-12, such as methylthio, ethylthio), an arylthio group (preferably 6-20 carbon atoms, more preferably 6-16 carbon atoms, still more preferably 6-12 carbon atoms, such as phenylthio) , Sulfonyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms) , More preferably 1 to 12 carbon atoms, such as mesyl and tosyl, sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, such as Methanesulfinyl, benzenesulfinyl), ureido group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenyl Ureido), a phosphoramido group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, such as diethylphosphoramido or phenylphosphorami) Hydroxy group, mercapto group, halogen atom (e.g., fluorine, chlorine, bromine, iodine), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, Heterocyclic groups (preferably 1 to 30 carbon atoms, more preferably carbon 1-12, its heteroatoms selected from nitrogen, oxygen and sulfur atoms, specifically imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimida Zolyl, benzothiazolyl, carbazolyl, azepinyl), silyl group (preferably 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, still more preferably 3 to 24 carbon atoms, such as trimethylsilyl , Triphenylsilyl). These substituents may further be substituted. If possible, the substituents may combine with each other to form a ring.

Among the above compounds, more preferable ones used in the present invention are those having a cyclic amido structure of the general formula (A).

In the above formula, X represents an oxygen atom, a sulfur atom or N-R (R represents a hydrogen atom or an alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group or heterocyclic group).

X is preferably an oxygen atom, an NH or an N-alkyl group, wherein the alkyl group preferably has up to 8 carbon atoms, such as methyl, ethyl, butyl. More preferably, X is an oxygen atom.

Z represents an atomic group capable of forming a 5-8 membered ring, preferably a 5 or 6 membered ring.

The structure constituting Z may have a substituent. Substitutable substituents include alkyl groups (preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n -Octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl), alkenyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 carbon atoms) To 8, such as vinyl, allyl, 2-butenyl, 3-pentenyl), an alkynyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 12, still more preferably 2 to 8, For example propargyl, 3-pentynyl, aryl groups (preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, still more preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, Naphthyl), amino group (preferably 0 to 20 carbon atoms, more preferably 0 to 12 carbon atoms, still more preferably 0 to 6 carbon atoms, such as amino and methyl Mino, dimethylamino, diethylamino, diphenylamino, dibenzylamino), an alkoxy group (preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 8 carbon atoms, Methoxy, ethoxy, butoxy), aryloxy group (preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, still more preferably 6 to 12 carbon atoms, such as phenyloxy, 2- Naphthyloxy), an acyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl), Alkoxycarbonyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl group (preferably Is 7-20 carbon atoms, More preferably, it is 7-16 carbon atoms, More preferably, Is 7 to 10 carbon atoms, such as phenyloxycarbonyl) and acyloxy group (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 10 carbon atoms, such as acetoxy , Benzoyloxy), acylamino group (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 10 carbon atoms, such as acetylamino, benzoylamino), alkoxycarbonylamino group ( Preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, more preferably 2 to 12 carbon atoms, such as methoxycarbonylamino, aryloxycarbonylamino group (preferably 7 to 20 carbon atoms) Dogs, more preferably 7 to 16 carbon atoms, still more preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino, and sulfonylamino groups (preferably 1 to 20 carbon atoms, more preferably 1 to 20 carbon atoms). 16, more preferably carbon 1-12, such as methanesulfonylamino, benzenesulfonylamino) sulfamoyl group (preferably 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, still more preferably 0 to 12 carbon atoms, For example sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, carbamoyl groups (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, For example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl), alkylthio groups (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably carbon atoms) 1-12, such as methylthio, ethylthio), an arylthio group (preferably 6-20 carbon atoms, more preferably 6-16 carbon atoms, still more preferably 6-12 carbon atoms, such as phenylthio) , Sulfonyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms) , More preferably 1 to 12 carbon atoms, such as mesyl and tosyl, sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, such as Methanesulfinyl, benzenesulfinyl), ureido group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenyl Ureido), a phosphoramido group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, such as diethylphosphoramido or phenylphosphorami) Hydroxy group, mercapto group, halogen atom (e.g., fluorine, chlorine, bromine, iodine), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, Heterocyclic groups (preferably 1 to 30 carbon atoms, more preferably carbon 1-12, its heteroatoms selected from nitrogen, oxygen and sulfur atoms, specifically imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimida Zolyl, benzothiazolyl, carbazolyl, azepinyl), silyl group (preferably 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, still more preferably 3 to 24 carbon atoms, such as trimethylsilyl , Triphenylsilyl). These substituents may further be substituted. If possible, the substituents may combine with each other to form a ring.

As the additive used in the present invention (ie, a compound capable of chemically interacting with the dye), a water-soluble or water-miscible compound is preferable. The water-soluble and water-miscible compound as used herein means that the solubility of the compound in water at 25 ° C. is at least 0.001% by weight, preferably at least 0.01% by weight.

The amount of the additive in the inkjet ink of the present invention is 0.001 to 30% by weight, preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight.

The additive used in the present invention contributes to the weather resistance of the ink of the present invention, which may have the same function as the functional ingredient described later. Therefore, the additive may be in the range of the functional ingredient.

Preferably, the additive is a mixture of a dye having a heterocyclic structure in a molar ratio of 1/1, and the lambda max of the visible absorption spectrum of the dilute aqueous solution having a concentration of up to 1 mmol / L is at least 5 nm than that containing no additive. More preferably at most 10 nm, even more preferably at most 20 nm. Further, in the absorption spectrum, epsilon (molecular absorption coefficient) is preferably 5% or more, preferably 10% or more, more preferably 20% or more.

The spectral change seen in the mixture demonstrates the intermolecular interaction of the additive and the dye and includes the λ max shift (for either the long wave side or the short wave side) and the ε change (increase or decrease) as described above. Preferably ε is reduced.

Although the specific example of the preferable additive (chemically interactable with a dye) used for this invention is shown below, this invention is not limited to this.

<2nd aspect of this invention>

The ink set inkjet ink set of the second aspect of the present invention contains a yellow ink containing one or more yellow inks having a specific absorbance ratio and a specific oxidation potential. Content of the specific yellow dye in a yellow ink becomes like this. Preferably it is 0.2-20 weight%, More preferably, it is 0.5-15 weight%.

In addition, the ink set of the present invention contains a black ink containing at least one such specific yellow dye. The content of the specific yellow dye in the black ink is preferably 0.1 to 60% by weight, more preferably 1 to 50% by weight. Black ink contains the other dye or pigment mentioned later, and the color tone is adjusted to become black.

In order to evaluate the weather resistance of the ink in the ink set of the present invention, the following method is used.

The ink to be analyzed is printed on a reflection medium, and the reflection concentration is measured through a status A filter. In the magenta region, one point of a sample having a reflection concentration (D _G ) of 0.90 to 1.10 is defined as the initial concentration of the ink, and the printed sample is forcibly faded by using an ozone fading tester which generates 5 ppm of ozone at all times. Measure the time (t) at which the reflection density of the faded sample is reduced to 80% of the initial reflection concentration (D _G ) of the original sample, and the acceleration fading rate constant (k _G ) is expressed by the relation "0.8 = exp (-k _G ㆍ t) ". In the present invention, the speed constant k _G of the ink is at most 5.0 × 10 ⁻² [hour ⁻¹ ], more preferably at most 1.0 × 10 ⁻² [hour ⁻¹ ], still more preferably at most 5.0 × It is desirable to design it to be 10 ^-3 [time- ¹ ].

In order to lower the fading rate constant of the ink used in the present invention, the dye of the ink is preferably characterized as follows: 1) The dye is hardly oxidized. Specifically, the oxidation potential of the dye is increased as described below (by increasing the electron withdrawing group or by utilizing an electron deficient heterocycle). 2) the initial oxidation reactivity of the dye is suppressed (prone to escape protons are not present around the dye or unstable cationic radicals around the dye). 3) The association rate of dye is increased, so that the oxidation frequency per molecule is lowered (the dye has an easy association structure). 4) The molecular structure of the dye is as hard as possible so that the molecular mobility of the dye is lowered (so that the structure of the dye does not have a long substituent having high mobility and fixes the ring in the structure).

When the yellow ink and the black ink in the ink set of the present invention are compared with each other in terms of their accelerated fading rate constant, it is preferable that the accelerated fading rate constant of the yellow ink is smaller than that of the black ink. This is preferable because it is easy to maintain the color balance of the image even when it is faded.

The ink set of the present invention may contain any other dye in addition to the above in order to obtain a full color image or to adjust the color tone of the formed image.

<3rd aspect of this invention>

The ink composition for ink jet recording of the third aspect of the present invention preferably contains a dye (at least a yellow dye or a black dye), a water miscible organic solvent, and a surfactant, and a betaine-based surfactant is preferable.

Betaine-based surfactants are compounds for surfactants having both a cationic moiety and an anionic moiety in their molecule. The cationic moiety includes an amine nitrogen atom, a boron atom having 4 bonds to a carbon atom and an atom of an aromatic heterocyclic ring and a person atom. Among them, the amine nitrogen atom and the nitrogen atom of the aromatic heterocycle are preferable. Especially preferred are quaternary nitrogen atoms. Examples of the anionic moiety include a hydroxy group, a thio group, a sulfonamido group, a sulfo group, a carboxyl group, an imido group, a phosphoric acid group and a phosphonic acid group. Among them, preferred are carboxyl groups and sulfo groups. The total charge of the surfactant molecule may be cationic, anionic or neutral, but is preferably neutral.

In particular, as a betaine surfactant used for this invention, the compound of General formula (6) is preferable.

In General formula (6), R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. L represents a divalent linking group. M represents a hydrogen atom, an alkali metal atom, an ammonium group, a protonated organic amine or a nitrogen-containing heterocyclic group, or a quaternary ammonium ion group, and when it is a counter ion for an ammonium ion having N atoms in the general formula, it is present as a cation I do not do this. q represents an integer of 1 or more; r represents the integer of 1-4. p represents an integer of 0 to 4; p + r is 3 or 4. When p + r is 4, the N atom in the general formula is a protonated ammonium atom (= N ⁺ =). When q is 2 or more, the COOM may be the same or different. When r is 2 or more, (L- (COOM) q) may be the same or different. When p is 2 or more, R may be same or different.

Among the compounds of the general formula (6) as the betaine-based surfactant used in the present invention, those of the following general formula (7) or (8) are more preferable.

Wherein R _1B to R _3B are each an alkyl group (substituted as necessary, preferably 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, cetyl, stearyl, oleyl) ), An aryl group (substituted as necessary, preferably 6 to 20 carbon atoms, such as phenyl, tolyl, xylyl, naphthyl, cumyl, dodecylphenyl), heterocyclic group (substituted as necessary, preferably Preferably 2 to 20 carbon atoms such as pyridyl, quinolyl); These may combine with each other and form ring structure. Among these, alkyl groups are more preferable. L represents a divalent linking group. Preferably, it is a bivalent coupling group containing an alkylene or arylene group as a basic structural unit. The linking chain portion of the group may contain a hetero atom such as oxygen, sulfur or nitrogen atom. R _1B to R _3B and L may be substituted with various substituents. Examples of the substituent include an alkyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 8 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n- Octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl), alkenyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to carbon atoms) 8, such as vinyl, allyl, 2-butenyl, 3-pentenyl, alkynyl groups (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 8 carbon atoms, for example Propargyl, 3-pentynyl), an aryl group (preferably from 6 to 30 carbon atoms, more preferably from 6 to 20 carbon atoms, still more preferably from 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, naph Tyl), amino group (preferably 0 to 20 carbon atoms, more preferably 0 to 12 carbon atoms, still more preferably 0 to 6 carbon atoms, such as amino and methyla) Furnace, dimethylamino, diethylamino, diphenylamino, dibenzylamino), an alkoxy group (preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 8 carbon atoms, Methoxy, ethoxy, butoxy), aryloxy group (preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, still more preferably 6 to 12 carbon atoms, such as phenyloxy, 2- Naphthyloxy), an acyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl), Alkoxycarbonyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl group (preferably Is 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, still more preferably 7 to 10 carbon atoms, such as phenyloxycarbonyl), an acyloxy group (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 10 carbon atoms such as acetoxy, Benzoyloxy), acylamino group (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 10 carbon atoms, such as acetylamino, benzoylamino), alkoxycarbonylamino group (preferably Preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, more preferably 2 to 12 carbon atoms, such as methoxycarbonylamino, aryloxycarbonylamino group (preferably 7 to 20 carbon atoms) More preferably 7 to 16 carbon atoms, more preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino, and sulfonylamino group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms). Dogs, more preferably carbon atoms 1-12, such as methanesulfonylamino, benzenesulfonylamino) sulfamoyl group (preferably 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, still more preferably 0 to 12 carbon atoms, For example sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, carbamoyl groups (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, For example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl), alkylthio groups (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably carbon atoms) 1-12, such as methylthio, ethylthio), an arylthio group (preferably 6-20 carbon atoms, more preferably 6-16 carbon atoms, still more preferably 6-12 carbon atoms, such as phenylthio) , Sulfonyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, Most preferably, 1 to 12 carbon atoms, such as mesyl and tosyl, sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, such as methane) Sulfinyl, benzenesulfinyl), ureido groups (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, such as ureido, methylureido, phenylurei) Fig.), Phosphoramido groups (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, such as diethylphosphoramido and phenylphosphoramido) ), Hydroxy group, mercapto group, halogen atom (e.g. fluorine, chlorine, bromine, iodine), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, complex Ventilation (preferably 1 to 30 carbon atoms, more preferably 1 carbon ˜12 and its heteroatoms are selected from nitrogen, oxygen and sulfur atoms, specifically imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl , Benzothiazolyl, carbazolyl, azepinyl), silyl group (preferably 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, still more preferably 3 to 24 carbon atoms, such as trimethylsilyl, Triphenylsilyl). These substituents may further be substituted. When two or more substituents have, they may be the same or different. If possible, the substituents may combine with each other to form a ring. One molecule of the compound may have a plurality of betaine structures bonded to each other through any one of R _1B to R _3B and L.

In the betaine surfactant used in the present invention, at least one of R _1B to R _3B and L contains a group having 8 or more carbon atoms. In particular, it is preferable that any one of R <_1B> -R <_3B> contains a long chain alkyl group.

(R) _p1 -N- [L- (COOM ¹ ) q] _r1 (8)

Wherein R, L and q have the same meanings as in the general formula (6). p1 represents the integer of 0-3, r1 represents the integer of 1-3. M ¹ represents an alkali metal ion or a hydrogen atom. p1 + r1 is 3. When p is 2 or more, R may be same or different.

General formula (6) and (8) are demonstrated below.

In the general formula, R is an alkyl group (substituted as necessary, preferably 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, cetyl, stearyl, oleyl) , An aryl group (substituted as necessary, preferably 6 to 20 carbon atoms, such as phenyl, tolyl, xylyl, naphthyl, cumyl, dodecylphenyl), a heterocyclic group (substituted as necessary, preferably Represents 2-20 carbon atoms, such as pyridyl, quinolyl); These may combine with each other and form ring structure. Among these, alkyl groups are more preferable.

L represents a divalent linking group. Preferably, it is a bivalent coupling group containing an alkylene or arylene group as a basic structural unit. The linking chain portion of the group may contain a hetero atom such as oxygen, sulfur or nitrogen atom.

R and L may be substituted with various substituents. Examples of the substituent include an alkyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 8 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n- Octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl), alkenyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to carbon atoms) 8, such as vinyl, allyl, 2-butenyl, 3-pentenyl, alkynyl groups (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 8 carbon atoms, for example Propargyl, 3-pentynyl), an aryl group (preferably from 6 to 30 carbon atoms, more preferably from 6 to 20 carbon atoms, still more preferably from 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, naph Yl), amino groups (preferably 0 to 20 carbon atoms, more preferably 0 to 12 carbon atoms, still more preferably 0 to 6 carbon atoms, such as amino, methylamino, Dimethylamino, diethylamino, diphenylamino, dibenzylamino), an alkoxy group (preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 8 carbon atoms, such as Oxy, ethoxy, butoxy), aryloxy group (preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, still more preferably 6 to 12 carbon atoms, such as phenyloxy, 2-naphthyl) Oxy), acyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl), alkoxycarbonyl group (Preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 12 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl), and an aryloxycarbonyl group (preferably carbon number) 7-20, More preferably, it is 7-16 carbon atoms, More preferably, burnt 7 to 10 minorities, such as phenyloxycarbonyl), acyloxy groups (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 10 carbon atoms such as acetoxy, Benzoyloxy), acylamino group (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 10 carbon atoms, such as acetylamino, benzoylamino), alkoxycarbonylamino group (preferably Preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, more preferably 2 to 12 carbon atoms, such as methoxycarbonylamino, aryloxycarbonylamino group (preferably 7 to 20 carbon atoms) More preferably 7 to 16 carbon atoms, more preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino, and sulfonylamino group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms). Dog, more preferably 1 to 12 carbon atoms For example, methanesulfonylamino, benzenesulfonylamino), sulfamoyl group (preferably 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, still more preferably 0 to 12 carbon atoms, such as sulfamoyl, Methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl), carbamoyl groups (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, such as carbamoyl) , Methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl), an alkylthio group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms) For example, methylthio, ethylthio), arylthio group (preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, still more preferably 6 to 12 carbon atoms, such as phenylthio), sulfonyl group ( Preferably it is 1-20 carbon atoms, More preferably, it is 1-16 carbon atoms, Furthermore, Preferably 1 to 12 carbon atoms, such as mesyl, tosyl, sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, such as methane alcohol Finyl, benzenesulfinyl), ureido group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, such as ureido, methyl ureido, phenyl ureido ), Phosphoramido groups (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, such as diethylphosphoramido and phenylphosphoramido) , Hydroxy group, mercapto group, halogen atom (e.g., fluorine, chlorine, bromine, iodine), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (Preferably 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms) Wherein the heteroatom is selected from nitrogen, oxygen and sulfur atoms, specifically imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzo Thiazolyl, carbazolyl, azepinyl), silyl groups (preferably from 3 to 40 carbon atoms, more preferably from 3 to 30 carbon atoms, still more preferably from 3 to 24 carbon atoms, such as trimethylsilyl, triphenyl Silyl) These substituents may further be substituted. When two or more substituents have, they may be the same or different. If possible, the substituents may combine with each other to form a ring. One molecule of the compound may contain a plurality of betaine structures bonded to each other via R or L.

M is a hydrogen atom, an alkali metal ion (e.g., sodium ion, potassium ion, lithium ion, cesium ion), ammonium ion or an amine organic cation (if it is a primary to tertiary amine, it is for example a protonated methylamine, Dimethylamine, ethylamine, diethylamine, triethylamine, diazabicycloundecene, diazabicyclooctane, piperidine, pyrrolidine, morpholine, N-methylpiperidine, N-methylpolporine, pyridine , Pyrazine, aniline, N, N-dimethylaniline, and when it is a quaternary ammonium salt, it represents, for example, tetramethylammonium ion, tetraethylammonium ion, trimethylbenzylammonium ion, methylpyridinium ion, benzylpyridinium ion). . In particular, it is preferable that M is an alkali metal ion or a hydrogen atom.

q is an integer of 1 or more (preferably at most 5, more preferably at most 2); r is an integer of 1-4 (preferably 1 or 2). k is an integer of 0 to 4; m is an integer of 1 or more (preferably up to 4, more preferably 1). p is an integer of 0-4 (preferably 1 or 2), and p + r is 3 or 4. When p + r is 4, the N atom in the formula is a quaternary ammonium cation and one M is a dissociated cation. When q is 2 or more, the COOM may be the same or different. When r is 2 or more, (L- (COOM) q) may be the same or different. When p is 2 or more, R ^k may be the same or different.

Preferably, R or L contains a hydrocarbon group of 8 or more carbon atoms. Among the compounds of the general formula (8), those most preferably used in the present invention are those of the following general formula (9).

R-N- (L- (COOM^One)₂ (9)

R, L and M ¹ have the same meanings as those of the general formula (8). The two (L-COOM ¹ ) may be the same or different. The two L and M ¹ may be the same or different. More preferably, R is an alkyl group and L is an alkylene group.

Preferred examples of the betaine surfactant used in the present invention are shown below. It goes without saying that the present invention is not limited to these.

The amount of the betaine surfactant in the ink composition may be any one as long as it can exhibit the effects of the present invention, but the ink composition is preferably 0.001 to 50% by weight, more preferably 0.1 to 20% by weight. In an ink set having two or more inks having the same color but different dye concentrations, the concentration of the betaine surfactant in the ink with the highest dye concentration is higher than that in the other inks with the lowest dye concentration. desirable. In particular, the concentration of the betaine surfactant in the ink is adjusted to the extent of the dye concentration of the ink, and it is more preferable that the betaine surfactant concentration is higher among the ink having the highest dye concentration.

For example, when the dye concentrations in the two inks A and B are Da and Db (Da> Db) and the betaine surfactant concentrations are Va and Vb (Va> Vb), Da / Db = k (Va / It is preferable that k of Vb) is within 0.1-10.

Inks used in the present invention are prepared by dissolving and / or dispersing a dye in water and a water miscible organic solvent. In particular, the ink is preferably an aqueous ink containing a water-soluble dye. In the ink set, inks different in color may contain a betaine surfactant.

General formula (1)-(5) is demonstrated in detail below.

[Dye of General Formula (1)]

In view of the fastness, in particular, the fastness to ozone gas, as the dye of the general formula (1), the following is preferable: the ink containing the dye is printed on the reflecting medium, and the reflectance concentration is measured through a status A filter. do. One point of the sample whose reflection concentration D _B is 0.90 to 1.10 in the yellow region is defined as the initial concentration of the ink, and the printed sample is forcibly discolored using an ozone fading tester which generates 5 ppm of ozone at all times. The time t at which the reflection density of the faded sample was reduced to 80% (the remaining ratio) of the initial concentration of the original sample was measured, and an accelerated fading rate constant k was derived from this. The rate constant of the dye for use in the present invention is preferably at most 5.0 × 10 ⁻² [hour ⁻¹ ], more preferably at most 3.0 × 10 ⁻² [hour ⁻¹ ], even more preferably at most 1.0 × 10 ^-2 [time ^-1 ].

Reflectance is measured through a status A filter (blue) using a reflectometer (X-Rite 310TR). The accelerated fading rate constant k is derived from the residual ratio = exp (-kt), i.e. k = (-ln 0.8) / k.

Particularly ozone gas, the yellow dye used in the present invention has an oxidation potential of more than 0.1 V (vs SCE), more preferably more than 1.1 V (vs SCE), more preferably more than 1.2 V (vs SCE). It is preferable from the viewpoint of the fastness to. As the form of the dye, an azo dye having a specific structure satisfying the above physical requirements is preferable.

Oxidation potential (Eox) of the dye can be easily measured by those skilled in the art. Measurement methods are described, for example, in P. Delahay, New Instrumental Methods in Electrochemistry , 1954, Interscience; Published by AJ Bard et al., Electrochemical Methods , 1980, John Wiley &Sons; A. Fujishima et al., Electrochemical Measurement Methods , 1984, published in Gihodo.

Specifically, the oxidation potential can be measured as follows: The sample to be analyzed is concentrated in a solvent such as dimethyl formamide or acetonitrile containing a supporting electrolyte such as sodium perchlorate or tetrapropylammonium perchlorate at a concentration of 1 × 10 ⁻⁶ to 1 Dissolve to 10 x ^{2 -2} mol / L, and measure its oxidation potential versus SCE (standard saturated caramel electrode) by cyclic voltammetry. The oxidation potential value may be off by about 10 millivolts due to the influence of the interpotential potential or the resistance of the sample solution, but may be corrected with a reference sample (for example, hydroquinone). In this way, the reproducibility of the potential value measured as described above is confirmed.

In the present invention, the oxidation potential of the dye is measured at a supported electrolyte and dimethylformamide containing 0.1 mol · dm ^{−3 of} tetrapropylammonium perchlorate (wherein the concentration of the dye is 0.001 mol · dm ⁻³ ). Define randomly.

Eox represents the electron mobility from the sample to the electrode. The higher the Eox value of the sample (those having a positive oxidation potential), the less likely the electrons move from it to the electrode, i.e. the more the sample is less oxidized. In relation to the structure of the compound, the compound has a positive oxidation potential by introducing an electron withdrawing group, while a negative oxidation potential is obtained by introducing an electron donor. In the present invention, it is preferable to introduce an electron withdrawing group into the skeleton of the yellow dye to give the dye a more positive oxidation potential to lower the reactivity of the dye with ozone in the form of an electrophilic agent.

In addition to good fastness, the dyes used in the present invention are preferred to impart good color, and more preferably, the long wavelength side shows a sharp ending tail profile in the absorption spectrum of the dye. Therefore, the λmax value of the yellow dye is in the range of 390 nm to 470 nm, and the ratio I (λ max +70 nm) / I of the absorbance I (λ max +70 nm) at (λ max +70 nm) to the absorbance I (λ max) at λ max. (λ max) is at most 0.2. More preferably, the ratio is 0.15, More preferably, it is a maximum of 0.10. Absorption wavelength and absorbance as defined herein are measured in solvents (water or ethyl acetate).

In General formula (1), A and B respectively independently represent the heterocyclic group substituted as needed. The heterocyclic ring is preferably 5-membered or 6-membered, and may have a monocyclic structure or a polycyclic structure formed by condensation of two or more rings, or may be an aromatic heterocycle or a non-aromatic heterocycle. As the hetero atom constituting the hetero ring, all N, O and S atoms are preferable. n is an integer selected from 1 or 2, Preferably it is 2. L represents a substituent bonded to any predetermined position of A or B. when n is 1, L is a hydrogen atom or a monovalent substituent; When n is 2, L is a chemical bond or a divalent linking group.

In the general formula (1), the heterocyclic ring of A is 5-pyrazolone, pyrazole, triazole, oxazolone, isoxoxazolone, barbituric acid, pyridone, pyridine, rhodanine, pyrazolidinedione, pyra Preference is given to condensed heterocycles formed by condensation of zolopyridone, meldmic acid and these heterocycles with any hydrocarbon aromatic or heterocycle. Among them, 5-pyrazolone, 5-aminopyrazole, pyridone, 2,6-diaminopyridine and pyrazoloazole are preferable; More preferred are 5-aminopyrazole, 2-hydroxy-6-pyridone and pyrazolotriazole.

Heterocycles of B include pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzo Thiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, isoxazole, benzoxazole, triazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, benzisoxazole , Pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline are preferred. Among these, more preferred are pyridine, quinoline, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, isoxazole, benzoxazole, thiazole, benzothiazole and isothia Sol, benzisothiazole, thiadiazole, benzisoxazole; More preferred are quinoline, thiophene, pyrazole, thiazole, benzoxazole, benzisoxazole, isothiazole, imidazole, benzothiazole, thiadiazole; Especially preferred are pyrazole, benzothiazole, benzoxazole, imidazole, 1,2,4-thiadiazole, 1,3,4-thiadiazole.

A and B may have a substituent, and examples of the substituent include halogen atom, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, alkoxy group, aryl Oxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryl Oxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, ar Real group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, imido group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, and later-mentioned A nonionic hydrophilic group.

Examples of the monovalent substituent of L include a substitutable substituent in A and B and an ionic hydrophilic group described later. Examples of the divalent linking group for L include an alkylene group, arylene group, heterocyclic moiety, -CO-, -SOn- (n is 0, 1 or 2), -NR- (R is a hydrogen atom, an alkyl group or an aryl group), -O- and other divalent groups in which these linking groups are combined are listed. These groups may have substituents such as those described above for A and B or ionic hydrophilic groups described below.

When the dye of formula (1) is used as a water-soluble dye, it is preferable that the dye has at least one ionic hydrophilic group in the molecule. Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a phosphono group and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group and a sulfo group are preferable; More preferably, they are a carboxyl group and a sulfo group. More preferably, the at least one ionic hydrophilic group is a carboxyl group. The carboxyl group, phosphono group and sulfo group may form a salt. Examples of counter ions that form salts include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions) and organic cations (eg, tetramethylammonium ions, tetramethylguanidium ions, tetramethylphosphonium ions). There is). As counter ion, alkali metal ion is preferable.

Among the dyes of the general formula (1), those in which a part of A-N = N-B is represented by the following general formula (I-A), (I-B) or (I-C) are preferable.

Wherein R 1 and R 3 each represent a hydrogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, an aryl group or an ionic hydrophilic group; R2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, a carbamoyl group, an acyl group, an aryl group or a heterocyclic group; R4 represents a heterocyclic group.

Wherein R 5 represents a hydrogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, an aryl group or an ionic hydrophilic group; Za represents -N =, -NH- or -C (R11) =: Zb and Zc each independently represent -N = or -C (R11) =; R11 represents a hydrogen atom or a nonmetallic substituent; R6 represents a heterocyclic group.

Wherein R 7 and R 9 each independently represent a hydrogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group or an ionic hydrophilic group; R8 is hydrogen atom, halogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, cyano group, acylamino group, sulfonylamino group, alkoxycarbonylamino group, ureido group, alkylthio group, arylthio group, alkoxycarbonyl group, carbon A barmoyl group, sulfamoyl group, sulfonyl group, acyl group, alkylamino group, arylamino group, hydroxy group or ionic hydrophilic group; R10 represents a heterocyclic group.

Examples of the alkyl groups of R 1, R 2, R 3, R 5, R 7, R 8, and R 9 in General Formulas (1-A), (1-B), and (1-C) include substituted alkyl groups and unsubstituted alkyl groups. Preferably, it is a C1-C20 alkyl group. Substituents for alkyl groups include hydroxy groups, alkoxy groups, cyano groups, halogen atoms and ionic hydrophilic groups. Alkyl groups include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl groups.

Cycloalkyl groups of R1, R2, R3, R5, R7, R8 and R9 include substituted cycloalkyl groups and unsubstituted cycloalkyl groups. Preferably, they are a C5-C12 cycloalkyl group. Substituents for the cycloalkyl group are ionic hydrophilic groups. Cycloalkyl groups include cyclohexyl groups. Aralkyl groups of R1, R2, R3, R5, R7, R8 and R9 include substituted aralkyl groups and unsubstituted aralkyl groups. Preferably it is a C7-20 aralkyl group. An aralkyl group substituent is an ionic hydrophilic group. Examples of aralkyl groups are benzyl and 2-phenethyl groups.

Examples of the aryl group for R 1, R 2, R 3, R 5, R 7, R 8, and R 9 include a substituted aryl group or an unsubstituted aryl group. Preferably, it is a C6-C20 aryl group. Examples of the substituent of the aryl group include a hydroxy group, an alkyl group, an alkoxy group, a halogen atom, a cyano group, a carbamoyl group, a sulfamoyl group, an alkylamino group, an acylamino group and an ionic hydrophilic group. Examples of aryl groups are phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl groups.

The alkylthio groups of R1, R2, R3, R5, R7, R8 and R9 include substituted alkylthio groups and unsubstituted alkylthio groups. Preferably it is a C1-C20 alkylthio group. Examples of the substituent of the alkylthio group are ionic hydrophilic groups. Examples of the alkylthio group include methylthio group and ethylthio group. The arylthio groups of R1, R2, R3, R5, R7, R8 and R9 include substituted arylthio groups and unsubstituted arylthio groups. Preferably they are a C6-C20 arylthio group. Examples of the substituent of the arylthio group include the same ones as in the aforementioned aryl group. Examples of the arylthio group are phenylthio group and p-tolylthio group.

The heterocyclic group of R 2 is preferably 5- or 6-membered and may be condensed with any other ring. As heteroatoms constituting the heterocycle, N, S and O are preferable. The heterocycle of the group may be an aromatic heterocycle or a nonaromatic heterocycle. The heterocycle may be further substituted. Examples of the substituent for the ring include the same ones as described above for the aryl group. Preferably, the heterocycle is a six-membered nitrogen-containing aromatic heterocycle, and preferred examples thereof are triazine, pyrimidine and phthalazine.

Halogen atoms of R 8 include fluorine, chlorine and bromine atoms. Examples of the alkoxy group of R1, R3, R5 and R8 include a substituted alkoxy group and an unsubstituted alkoxy group. Preferably, it is a C1-C20 alkoxy group. Examples of the substituent of the alkoxy group include a hydroxy group and an ionic hydrophilic group. Examples of alkoxy groups include methoxy, ethoxy, isopropoxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy groups.

Examples of the aryloxy group for R 8 include a substituted aryloxy group and an unsubstituted aryloxy group. Preferably, it is a C6-C20 aryloxy group. Examples of the substituent of the aryloxy group include the same ones as those of the aryloxy group described above. Examples of aryloxy groups are phenoxy, p-methoxyphenoxy and o-methoxyphenoxy groups. Examples of the acylamino group for R 8 include a substituted acylamino group and an unsubstituted acylamino group. Preferably, it is a C2-C20 acylamino group. Examples of the substituent of the acylamino group include the same as those of the aryl group described above. Examples of acylamino groups are acetamido, propionamido, benzamido and 3,5-disulfobenzamido groups.

Examples of the sulfonylamino group for R 8 include an alkylsulfonylamino group, an arylsulfonylamino group and a heterocyclic sulfonylamino group, and the alkyl group moiety, the aryl group moiety and the heterocyclic moiety may have a substituent. Examples of these substituents are the same as those of the aryl group described above. Preferably, it is a C1-C20 sulfonylamino group. Examples of sulfonylamino groups include methylsulfonylamino and ethylsulfonylamino groups. Examples of the alkoxycarbonylamino group for R 8 include a substituted alkoxycarbonylamino group and an unsubstituted alkoxycarbonylamino group. Preferably, it is a C2-C20 alkoxycarbonylamino group. Examples of the substituent of the alkoxycarbonylamino group are ionic hydrophilic groups. Examples of the alkoxycarbonylamino group are ethoxycarbonylamino groups.

Examples of the ureido group for R 8 include a substituted ureido group and an unsubstituted ureido group. Preferably, it is a ureido group having 1 to 20 carbon atoms. Examples of the substituent of the ureido group include an alkyl group and an aryl group. Examples of ureido groups include 3-methylureido, 3,3-dimethylureido and 3-phenylureido groups.

Examples of the alkoxycarbonyl group for R7, R8 and R9 include a substituted alkoxycarbonyl group and an unsubstituted alkoxycarbonyl group. Preferably, it is a C2-C20 alkoxycarbonyl group. Examples of the substituent of the alkoxycarbonyl group are ionic hydrophilic groups. Examples of alkoxycarbonyl groups are methoxycarbonyl and ethoxycarbonyl groups.

Carbamoyl groups of R2, R7, R8 and R9 include substituted carbamoyl groups and unsubstituted carbamoyl groups. Examples of the substituent of the carbamoyl group include an alkyl group. Examples of carbamoyl groups are methylcarbamoyl and dimethylcarbamoyl groups.

The sulfamoyl group of R8 includes a substituted sulfamoyl group and an unsubstituted sulfamoyl group. Examples of the substituent of the sulfamoyl group include an alkyl group. Examples of sulfamoyl groups are dimethylsulfamoyl and di- (2-hydroxyethyl) sulfamoyl groups.

Examples of the sulfonyl group for R 8 include an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic sulfonyl group, and these may further have a substituent. Examples of substituents are ionic hydrophilic groups. Examples of sulfonyl groups are methylsulfonyl and phenylsulfonyl groups.

The acyl groups of R2 and R8 include substituted acyl groups and unsubstituted acyl groups. Preferably, it is an acyl group having 1 to 20 carbon atoms. Examples of the substituent of the acyl group include an ionic hydrophilic group. Examples of acyl groups are acetyl and benzoyl groups.

Examples of the amino group for R 8 include a substituted amino group and an unsubstituted amino group. Examples of the substituent of the amino group include an alkyl group, an aryl group and a heterocyclic group. Examples of amino groups include methylamino, diethylamino, anilino and 2-chloroanilino groups.

The heterocyclic group of R4, R6 and R10 may be the same as the heterocyclic group which is substituted as needed of B in General formula (1). Preferred examples, more preferred examples and more preferred examples thereof include the same as those described above as the group of B. Specifically, as the substituent of the heterocyclic group, for example, an ionic hydrophilic group, an alkyl group having 1 to 12 carbon atoms, an aryl group, an alkyl or arylthio group, a halogen atom, a cyano group, a sulfamoyl group, a sulfoneamino group, a carbamoyl group and an acylamino group Are listed. The alkyl group and the aryl group may be further substituted.

In formula (1-B), Za represents -N =, -NH- or -C (R11) =; Zb and Zc each independently represent -N = or -C (R11) =; R11 represents a hydrogen atom or a nonmetallic substituent. As the nonmetallic substituent of R 11, a cyano group, a cycloalkyl group, an aralkyl group, an aryl group, an alkylthio group, an arylthio group and an ionic hydrophilic group are preferable. These substituents may have the same meaning as the substituent of R1, and the preferable examples thereof may also be the same as those of R1. The example of the skeleton of the heterocyclic ring which consists of two 5-membered rings in general formula (1-B) is shown below.

As an example of the substituent of the group substituted by the said need, the above-mentioned thing is mentioned as group substituted as needed of the hetero rings A and B in General formula (1) mentioned above.

Among the dyes of the general formulas (1-A), (1-B) and (1-C), those of the general formula (1-A) are preferable, and those of the following general formula (1-A1) are more preferable.

Wherein R ²¹ and R ²³ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group or an aryl group; R ²² represents a hydrogen atom, an aryl group or a heterocyclic group; One of X and Y represents a nitrogen atom, and the other represents —CR ²⁴ ; R ²⁴ is hydrogen atom, halogen atom, cyano group, alkyl group, alkylthio group, alkylsulfonyl group, alkylsulfinyl group, alkyloxycarbonyl group, carbamoyl group, alkoxy group, aryl group, arylthio group, arylsulfonyl group, arylsulfi A silyl group, an aryloxy group, or an acylamino group is shown. Among them, a hydrogen atom, an alkyl group, an alkyl or arylthio group, and an aryl group are preferable; More preferred are hydrogen atoms, alkylthio groups and aryl groups. These substituents may further be substituted.

Preferred examples of the dyes used in the present invention are described in Japanese Patent Application Nos. 2003-286844 and 2003-277662, 2003-277661, 2003-128953 and 2003-41160. However, the dye used for this invention is not limited to these. These compounds can be manufactured with reference to the said patent document and Unexamined-Japanese-Patent No. 2-24191 and 2001-279145.

_

In the present invention, the yellow ink preferably contains 0.2 to 20% by weight, more preferably 0.5 to 15% by weight of the dye of the general formula (1).

[Dye of General Formula (2)]

Phthalocyanine dyes used in conventional inkjet inks are derived from sulfonation of unsubstituted phthalocyanine, and thus, the number and position of substituents of the mixed compounds cannot be specifically determined. And it is characterized in that the position can be specifically determined.

Preferred embodiments of the cyan ink containing this type of dye are described below.

1) Cyan ink was printed on Epson's PM photographic paper to form an image, and a part of the image having a reflection density OD of 1.0 was exposed to xenon light (Xe 1.1 W / m, intermittent exposure) for 3 days through a TAC filter. The cyan ink whose pigment | dye persistence (discoloration density / initial stage x100) is 90% or more.

2) When the cyan ink is printed to form an image, and a part of the image having a cyan reflection concentration of 0.9 to 1.1 is left in a 5 ppm ozone environment for 24 hours through a status A filter, the remaining pigment ratio (fading concentration / minimum concentration). Cyan ink having at least 60%, preferably at least 80%.

3) Cyan ink in which the amount of Cu ions flowing into the water after fading the image formed with cyan ink under ozone under 2) is up to 20% of the total dye.

4) Cyan ink in which cyan ink can penetrate more than 30% of the upper layer of a specific water phase.

In formula (2), X ₂₁ , X ₂₂ , X ₂₃ and X ₂₄ are each independently -SO-Z ₂ , -SO ₂ -Z ₂ , -SO ₂ NR ₂₁ R ₂₂ , a sulfo group, -CONR ₂₁ R ₂₂ or -CO ₂ R ₂₁ is represented. Among these substituents, -SO-Z ₂ , -SO ₂ -Z ₂ , -SO ₂ NR ₂₁ R ₂₂ and -CONR ₂₁ R ₂₂ are preferred; More preferred are -SO ₂ -Z ₂ and -SO ₂ NR ₂₁ R ₂₂ ; Most preferably -SO ₂ -Z ₂ . When either one of a ₂₁ to a ₂₄ indicating the number of substituents is 2 or more, a plurality of X ₂₁ to X ₂₄ may be the same or different, and each independently represent any one of the groups described above. X ₂₁ , X ₂₂ , X ₂₃ and X _{24 may} all be the same substituent; Or in the form of a substituent the same, may be part of or different substituents, for example, X _21, X _22, X ₂₃ and X _24, but all of the same -SO ₂ -Z _2, Z ₂ in the substituent or different from each other, ; Alternatively, the substituents may be different from each other, for example, may contain different -SO ₂ -Z ₂ and -SO ₂ NR ₂₁ R ₂₂ .

Z ₂ independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Preferably, it is a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. Most preferably, it is a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group.

R ₂₁ and R ₂₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group. A substituted heterocyclic group is shown. Preferably, they are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. More preferably, they are a hydrogen atom, a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group. However, it is not preferable that both R ₂₁ and R ₂₂ are hydrogen atoms.

As a substituted or unsubstituted alkyl group of R ₂₁ , R ₂₂ and Z ₂ , an alkyl group having 1 to 30 carbon atoms is preferable. Especially in order to increase dye solubility and ink stability, a branched alkyl group is more preferable. More preferably a group having an asymmetric carbon atom (dye is used as the racemate). Substituents for the groups include those similar to those described above as substitutable groups for Z ₂ , R ₂₁ , R ₂₂ , Y ₂₁ , Y ₂₂ , Y ₂₃ and Y ₂₄ . Among them, hydroxyl groups, ether groups, ester groups, cyano groups, amido groups and sulfonamide groups are particularly preferable because they increase dye association and improve dye fastness. In addition to these, the group may be substituted with a halogen atom or an ionic hydrophilic group. The carbon number of the said alkyl group does not contain the carbon number of the substituent of the said group, and it is the same also about another group.

As for carbon number of the substituted or unsubstituted cycloalkyl group of R <_21> , R <_22> and Z <_2> , 5-30 are preferable. In particular, in order to increase dye solubility and ink stability, groups having an asymmetric carbon atom are preferred (dyes are used as racemates). Substituents for the groups include the same as the above-described substitutable groups for Z ₂ , R ₂₁ , R ₂₂ , Y ₂₁ , Y ₂₂ , Y ₂₃ and Y ₂₄ . Especially, a hydroxyl group, an ether group, ester group, cyano group, amido group, and sulfonamide group are especially preferable because it improves dye association and improves dye fastness. In addition to these, the group may be substituted with a halogen atom or an ionic hydrophilic group.

As a substituted or unsubstituted alkenyl group of R ₂₁ , R ₂₂ and Z _2, an alkenyl group having 2 to 30 carbon atoms is preferable. In particular, in order to increase dye solubility and ink stability, branched alkenyl groups are more preferable. More preferably a group having an asymmetric carbon atom (dye is used as the racemate). Substituents for the groups include those similar to those described above as substitutable groups for Z ₂ , R ₂₁ , R ₂₂ , Y ₂₁ , Y ₂₂ , Y ₂₃ and Y ₂₄ . Among them, hydroxyl groups, ether groups, ester groups, cyano groups, amido groups and sulfonamide groups are particularly preferable because they increase dye association and improve dye fastness. In addition to these, the group may be substituted with a halogen atom or an ionic hydrophilic group.

It is preferable that carbon number of the substituted or unsubstituted aralkyl group of R <_21> , R <_22> and Z <_2> is 7-30. In order to increase dye solubility and ink stability in particular, branched aralkyl groups are more preferable. More preferably a group having an asymmetric carbon atom (dye is used as the racemate). Examples of the substituents on the group _{include, Z 2, R 21, R} 22, Y 21, Y 22, Y 23 and are identical to those listed above as the substituent of Y _24. Among them, hydroxyl groups, ether groups, ester groups, cyano groups, amido groups and sulfonamide groups are particularly preferable because they increase dye association and improve dye fastness. In addition to these, the group may be substituted with a halogen atom or an ionic hydrophilic group.

As a substituted or unsubstituted aryl group of R ₂₁ , R ₂₂ and Z _2, an aryl group having 6 to 30 carbon atoms is preferable. Examples of the substituents on the group _{include, Z 2, R 21, R} 22, Y 21, Y 22, Y 23 and are identical to those listed above as the substituent of Y _24. Among them, electron attracting is particularly preferable because it quantifies the oxidation potential of the dye and improves the fastness of the dye. The electron withdrawing group has a positive σ p value and a Hammett substituent constant. Among them, halogen atom, heterocyclic group, cyano group, carboxyl group, acylamino group, sulfonamido group, sulfamoyl group, carbamoyl group, sulfonyl group, amido group, acyl group, sulfo group and quaternary ammonium group are preferable; More preferably, they are cyano group, carboxyl group, sulfamoyl group, carbamoyl group, sulfonyl group, imido group, acyl group, sulfo group and quaternary ammonium group.

As a heterocyclic group of R <_21> , R <_22> and Z <_2> , it is preferable that it is 5- or 6-membered, and may be condensed with another ring. An aromatic heterocyclic group or a non-aromatic heterocyclic group may be sufficient. Examples of the heterocyclic group of R ₂₁ , R _22, and Z ₂ are shown below in the form of a heterocycle omitting the substitution position. In these groups, the substitution position is not limited. For example, pyridine may have a substituent in any of the 2, 3 or 4 positions. Examples of heterocycles include pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene , Pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, blood There are lollidine, piperidine, piperazine, imidazolidine, thiazoline. Of these, aromatic heterocyclic groups are preferred. Examples of the above examples include pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole, thiazole, benzothiazole, isothiazole, and benziisothiazole. And thiadiazole. These may be substituted further. Examples of these substituents include those described above as substituents for Z ₂ , R ₂₁ , R ₂₂ , Y ₂₁ , Y ₂₂ , Y ₂₃ and Y ₂₄ . These preferable substituents may be the same as those of the said aryl group; More preferred substituents are the same as those described above for the aryl group.

Y ₂₁ , Y ₂₂ , Y ₂₃ and Y ₂₄ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, an amino group, an alkylamino group , Alkoxy group, aryloxy group, acylamino group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxy Carbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imido group, heterocyclic thio group, phosphoryl group, acyl group, carboxyl group or sul Indicates abandonment. These groups may be further substituted.

Among them, hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, alkoxy group, amido group, ureido group, sulfonamido group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, carboxyl group and sulfo group are preferable; More preferably a hydrogen atom, a halogen atom, a cyano group, a carboxyl group and a phosphor group; Hydrogen atoms are most preferred.

Examples of the substituent of the substitutable group of Z ₂ , R ₂₁ , R ₂₂ , Y ₂₁ , Y ₂₂ , Y ₂₃ and Y ₂₄ are shown below.

Straight or branched alkyl groups of 1 to 12 carbon atoms, straight or branched aralkyl groups of 7 to 18 carbon atoms, straight or branched alkenyl groups of 2 to 12 carbon atoms, straight or branched alkynyl groups of 2 to 12 carbon atoms , A linear or branched cycloalkyl group having 3 to 12 carbon atoms, a linear or branched cycloalkenyl group having 3 to 12 carbon atoms (since it increases dye solubility and ink stability, these groups are preferably branched, more preferably Specific examples of these groups include methyl, ethyl, propyl, isopropyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoro Romethyl, cyclopentyl); Halogen atoms (eg chlorine, bromine), aryl groups (eg phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl), heterocyclic groups (eg imidazolyl, pyrazolyl, triazolyl , 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group, carboxyl group, amino group, alkyloxy group (e.g. methoxy, ethoxy, 2-meth) Methoxyethoxy, 2-methanesulfonylethoxy), aryloxy groups (e.g., phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarba Moylphenoxy, 3-methoxycarbamoylphenoxy), acylamino groups (e.g. acetamido, benzamido, 4- (3-t-butyl-4-hydroxyphenoxy) butanamido), alkyl Amino groups (eg methylamino, butylamino, diethylamino, methylbutylamino), anilino groups (eg phenylamino, 2-chloroanilino), ureido groups (eg phenylureido, methylureido, N, N-dibutylurey ), Sulfamoylamino group (e.g., N, N-dipropylsulfamoylamino), alkylthio group (e.g., methylthio, octylthio, 2-phenoxyethylthio), arylthio group (e.g., phenylthio, 2- Butoxy-5-t-octylphenylthio, 2-carboxyphenylthio), alkyloxycarbonylamino group (e.g. methoxycarbonylamino), sulfonamido group (e.g. methanesulfonamido, benzenesulfonamido, p Toluenesulfonamido), carbamoyl groups (e.g., N-ethylcarbamoyl, N, N-dibutylcarbamoyl), sulfamoyl groups (e.g., N-ethylsulfamoyl, N, N-dipropylsulfa Moyl, N-phenylsulfamoyl), sulfonyl groups (e.g. methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkyloxycarbonyl groups (e.g. methoxycarbonyl, butyloxycarbonyl), heterocyclic Oxy group (eg 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), azo groups (eg phenylazo, 3-methoxyphenylazo, 4-pibal Monoaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy group (e.g. acetoxy), carbamoyloxy group (e.g. N-methylcarbamoyloxy, N-phenylcarbamoyl) Oxy), silyloxy groups (e.g. trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino groups (e.g. phenoxycarbonylamino), imido groups (e.g., N-succinimido, N-phthalimide Fig.), Heterocyclic thi groups (e.g. 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), sulfinyl groups (e.g. , 3-phenoxypropylsulfinyl), phosphonyl group (e.g. phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (e.g. phenoxycarbonyl), acyl group (e.g. acetyl, 3-phenylpropanoyl, benzoyl), ionic hydrophilic groups (eg, carboxy, sulfo, phosphono, quaternary ammonium).

When the phthalocyanine dye of the general formula (2) is soluble in water, the dye preferably has an ionic hydrophilic group. Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a phosphono group and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group and a sulfo group are preferable; More preferred are carboxyl groups and sulfo groups. Carboxyl, phosphono and sulfo groups may form salts. Examples of counter ions that form salts include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions) and organic cations (eg, tetramethyl). Ammonium ion, tetramethylguanidium ion, tetramethylphosphonium ion). As the counter ion, an alkali metal salt is preferable. Lithium salts are more preferred because they increase dye solubility and ink stability.

As the number of ionic hydrophilic groups in the phthalocyanine dye, a dye having two or more ionic hydrophilic groups per dye molecule is preferable, and a dye having two or more sulfo and / or carboxyl groups is more preferable.

In the formula _{(2), a 21 ~ a} 24 and b ₂₁ ~ b ₂₄ denotes the number of substituents of X ₂₁ ~ X ₂₄ and Y ₂₁ ~ Y _24, respectively. a ₂₁ to a ₂₄ each independently represent a number of 0 to 4, but all of them are not 0 at the same time. b ₂₁ ~ b ₂₄ independently represent a number of 0-4 respectively. When a ₂₁ to a ₂₄ and b ₂₁ to b ₂₄ are two or more numbers, a plurality of X ₂₁ to X ₂₄ and Y ₂₁ to Y ₂₄ are present in the formula, and they may be the same or different.

a ₂₁ and b ₂₁ satisfy the relationship a ₂₁ + b ₂₁ = 4. More preferably, a ₂₁ is 1 or 2, and b ₂₁ is a combination of 3 or 2, respectively. Most preferably, the combination is such that a ₂₁ is 1 and b ₂₁ is 3.

The combination of a ₂₁ and b ₂₁ can likewise be applied to other combinations of a ₂₂ and b ₂₂ , a ₂₃ and b ₂₃ , a ₂₄ and b ₂₄ . Preferred embodiments of other combinations enumerate the same as those described above with the combination of a ₂₁ and b ₂₁ .

M represents a hydrogen atom, a metal atom or an oxide, hydrate or halide thereof.

M is preferably a hydrogen atom or Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Metal elements such as Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi are preferred. As the oxide, VO or GeO is preferable. As the hydrate, Si (OH) ₂ , Cr (OH) ₂ or Sn (OH) ₂ is preferable. Preferred halides are AlCl, SiCl ₂ , VCl, VCl ₂ , VOCl, FeCl, GaCl or ZrCl. Especially, Cu, Ni, Zn, and Al are more preferable; Most preferred is Cu.

The phthalocyanine dye of the general formula (2) may form a dimer (eg, Pc-MLM-Pc) or a trimer in which two or three Pc (phthalocyanine ring) molecules are bonded to each other through L (bivalent linking group). good. Among these, M may be the same or different.

As the divalent linking group for L, oxy group -O-, thio -S-, carbonyl group -CO-, sulfonyl group -SO _2- , imino group -NH-, methylene group -CH ₂ -or a combination thereof is preferable.

As a preferable combination of the substituent of the compound of General formula (2), it is preferable that 1 or more substituents are the preferable group mentioned above. More preferably, a plurality of substituents are the above-mentioned preferred groups. Most preferably, all of the substituents are those mentioned above.

It is more preferable to have a structure of the said General formula (5) among the phthalocyanine dye of General formula (2). The phthalocyanine dye of General formula (5) is demonstrated in detail below.

In General Formula (5), X ₅₁ to X ₅₄ and Y ₅₁ to Y ₅₈ have the same meanings as X ₂₁ to X ₂₄ and Y ₂₁ to Y ₂₄ of General Formula (2). The preferable example is the same as that mentioned later. M ₁ has the same meaning as M in General Formula (2), and preferred examples thereof are the same as those described later.

In formula (5), a ₅₁ to a ₅₄ each independently represent an integer of 1 or 2, preferably 4 ≦ a ₅₁ + a ₅₂ + a ₅₃ + a ₅₄ ≦ 6, and more preferably a ₅₁ = a ₅₂ = a ₅₃ = a ₅₄ = 1.

X ₅₁ , X ₅₂ , X ₅₃ and X ₅₄ may all be the same substituent; Or may be part of the type of the substituents the same or different substituents, for example, X _51, X _52, X ₅₃ and X _54, but all of the same -SO ₂ -Z _2, Z ₂ in the substituent or different from each other; Or the substituents may be different from each other, for example, -SO ₂ -Z ₂ and -SO ₂ NR ₂₁ R ₂₂ .

It shows below about the combination of the especially preferable substituent of the phthalocyanine dye of General formula (5).

X ₅₁ to X ₅₄ independently represent -SO-Z ₅ , -SO ₂ -Z ₅ , -SO ₂ NR ₅₁ R ₅₂ , or -CONR ₅₁ R ₅₂ , preferably -SO ₂ -Z ₅ or -SO ₂ NR ₂₁ R ₂₂ , most preferably -SO ₂ -Z ₅ .

Preferably, Z ₅ is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. More preferably, it is a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group. In addition, in order to further improve dye solubility and ink stability, the substituent preferably has an asymmetric carbon atom (a dye is used as a racemate). In addition, in order to improve dye association and dye fastness, the substituent preferably has any one of a hydroxy group, an ether group, an ester group, a cyano group, an amido group, and a sulfonamide group.

Preferably, R ₅₁ and R ₅₂ are independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. More preferably, it is either a hydrogen atom, a substituted alkyl group, a substituted aryl group, or a substituted heterocyclic group. However, it is not preferable that both R ₅₁ and R ₅₂ are hydrogen atoms. Also preferably, in order to further improve dye solubility and ink stability, the substituent preferably has an asymmetric carbon atom (a dye is used as the racemate). In addition, in order to improve dye association and dye fastness, the substituent preferably has any one of a hydroxy group, an ether group, an ester group, a cyano group, an amido group and a sulfonamide group.

Y ₅₁ to Y ₅₈ are preferably hydrogen atoms, halogen atoms, alkyl groups, aryl groups, cyano groups, alkoxy groups, amido groups, ureido groups, sulfonamido groups, carbamoyl groups, sulfamoyl groups, alkoxycarbonyl groups and carboxyl groups Or a sulfo group, more preferably a hydrogen atom, a halogen atom, a cyano group, a carboxyl group or a sulfo group, and most preferably a hydrogen atom.

a ₅₁ to a ₅₄ are preferably independently 1 or 2, and more preferably all 1.

M ₁ is a hydrogen atom or a metal atom or an oxide, hydrate or halide thereof, preferably Cu, Ni, Zn or Al, and more preferably Cu.

When the phthalocyanine dye of the general formula (5) is soluble in water, the dye preferably has an ionic hydrophilic group. Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a phosphono group and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group and a sulfo group are preferable; More preferably, they are a carboxyl group and a sulfo group. Carboxyl, phosphono and sulfo groups may form salts. Examples of counter ions that form the salts include ammonium ions, alkali metal ions (e.g. lithium ions, sodium ions, potassium ions) and organic cations (e.g. tetra Methyl ammonium ion, tetramethylguanidium ion, tetramethylphosphonium ion). As the counter ion, an alkali metal salt is preferable. Lithium salts are more preferred because they increase dye solubility and ink stability.

As the number of ionic hydrophilic groups in the phthalocyanine dye, a dye having two or more ionic hydrophilic groups per dye molecule is preferable, and a dye having two or more sulfo and / or carboxyl groups is more preferable.

As a preferable combination of the substituent of the compound of General formula (5), it is preferable that 1 or more substituents are the said preferable substituents, More preferably, many substituents are the said preferable substituents. Most preferably all substituents are those preferred substituents.

As the chemical structure of the phthalocyanine dye of the general formula (5), each of the four benzene rings of the phthalocyanine skeleton is an electron such as a sulfinyl group, sulfonyl group or sulfamoyl group such that the sum of sigma p values of all substituents of the phthalocyanine skeleton is 1.6 or more. It is preferable to have one or more haulers.

The Hammet substituent constant sigma p is briefly described. Harvet's law was proposed by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, and its validity has been recognized in the field so far. Substituent constants obtained by the Hammet law have two values of sigma p and sigma m, which can be seen in a number of categories. See, for example, JA Dean, Lange's Handbook of Chemistry , 12th edition, 1979 (McGraw-Hill published); And Chemical Region is shown in the jeunggan, No.122, details on pp.96 ~ 103, 1979 (Nanko- do Publishing).

In the phthalocyanine dye of the general formula (2), in general, the position and number of substituents Xn (n is 1 to 4) and Ym (m is 1 to 4) are inevitably different depending on the preparation method thereof, that is, the dye It is usually in the form of a mixture. Thus, the general formula of the dye is shown by statistically averaging the mixture of these paramagnetics. The inventors classified such analogue mixtures into three types shown below, and found that a particular type of mixture was particularly preferable. Specifically, the phthalocyanine dye analog mixtures of the general formulas (2) and (5) were classified into the following three types based on the positions of the substituents. Y ₅₁ , Y ₅₂ , Y ₅₃ , Y ₅₄ , Y ₅₅ , Y ₅₆ , Y ₅₇ and Y ₅₈ in the general formula (5) are positioned at 1, 4, 5, 8, 9, 12, 13 or 16 positions, respectively. Located.

(1) β-substituted phthalocyanine dyes having a specific substituent at the 2 and / or 3 position, 6 and / or 7 position, 10 and / or 11 position, 14 and / or 15 position.

(2) α-substituted phthalocyanine dyes having a specific substituent at 1 and / or 4 position, 5 and / or 8 position, 9 and / or 12 position, 13 and / or 16 position.

(3) α, β-substituted phthalocyanine dyes having specific substituents at regular positions in 1 to 16 positions.

In the present specification, when describing phthalocyanine dye derivatives having different structures (particularly in terms of substitution positions), expressions of β-substituted, α-substituted and α, β-substituted phthalocyanine dyes are used.

Phthalocyanine dyes used in the present invention include, for example, Phthalocyanines-Chemistry and Function , Shirai & Kobayashi, pp.1-62 (IPC), and CC Lenznoff & ABP Lever, Phthalocyanines-Propeties and Applications , pp.1-54 (VCH). According to methods described or cited in, or according to methods analogous to these methods.

Phthalocyanine compounds of the general formula (2) used in the present invention are, for example, as described in WO 00/17275, 00/08103, 00/08101, 98/41853 and Japanese Patent Application Laid-Open No. 10-36471. It may be prepared through sulfonation, sulfonylchloride or amidation of substituted phthalocyanine compounds. In this case, sulfonation may occur at any position of the phthalocyanine nucleus, and it is difficult to control the number of positions to be sulfonated. Therefore, in the case of introducing the sulfo group under the reaction conditions of the preparation, it is not possible to specifically control the position and number of the introduced sulfo groups, thereby producing a mixture of analogs having different positions and numbers of substituents. Therefore, when the compound used in the present invention is prepared from the product prepared by the above method, the number and position of the heterocyclic substituted sulfamoyl group introduced into the compound cannot be specifically controlled, and thus used in the present invention thus prepared. The phthalocyanine dye to be obtained is in the form of a mixture of α, β-substituted groups having different numbers and positions of substituents.

For example, as described above, the more the electron withdrawing groups such as the sulfamoyl group are introduced into the phthalocyanine nucleus, the more the oxidation potential of the obtained dye becomes more positive and its ozone resistance also increases. However, according to the above production method, it is inevitable that the product contains a phthalocyanine dye with a negative oxidation potential because of the low introduction of electron withdrawing groups. Therefore, in order to improve the ozone resistance of the dye, it is preferable to use a production method that suppresses the production of a compound having a more negative oxidation potential.

According to the following reaction formula, the phthalocyanine compound of the general formula (5) is reacted with, for example, a phthalonitrile derivative (compound P) and / or a diiminoisoindolin derivative (compound Q) with a metal derivative of the general formula (6) Or Or a tetrasulfophthalocyanine compound obtained by reacting a 4-sulfophthalic acid derivative (Compound R) with a metal derivative of the general formula (6).

In the above formula, Xp corresponds to X ₅₁ , X ₅₂ , X ₅₃ or X ₅₄ in formula (5); Yq and Yq 'correspond to Y ₅₁ , Y ₅₂ , Y ₅₃ , Y ₅₄ , Y ₅₅ , Y ₅₆ , Y ₅₇ or Y ₅₈ , respectively. For compound R, M 'represents a cation.

As a cation of M ', Alkali metal cations, such as Li, Na, K; And organic cations such as triethylammonium ion and pyridinium ion.

M- (Y) d (6)

In the formula (6), M has the same meaning as that of M ₁ and M in the formula (5) in the formula (2); Y represents a monovalent or divalent ligand such as a halogen atom, an acetate anion, an acetylacetonate group or an oxygen atom; d represents the integer of 1-4.

Therefore, according to the manufacturing method mentioned above, a desired number of substituents can be introduced into the dye. In particular, in the case where a large number of electron withdrawing groups are introduced into the dye in order to increase the oxidation potential of the dye as in the present invention, the production method is much superior to the production method for producing the phthalocyanine compound of the general formula (2).

The phthalocyanine compound of the general formula (5) thus obtained is usually in the form of a mixture of the compounds of the following general formulas (a) -1 to (a) -4, i.e., β-substituted compounds, which are isomers at the substitution position of Xp.

If in the method both the Xp of the starting compound are the same, the X _51, X _52, X ₅₃ or X ₅₄ β- substituted phthalocyanine dyes are both the same substituent can be obtained. On the other hand, in the above method, when Xp is used in combination with different starting compounds, it is possible to obtain dyes having the same kind but partially different dyes or different kinds of substituents. Of the dyes of the formula (5), dyes having other electron withdrawing groups are particularly preferred because they can control the solubility, associability of the dyes, and the storage stability of the ink containing the dyes in a desired manner.

Although the detailed cause is not clear, the β-substituted dye tends to be clearly superior in color, light fastness and ozone gas resistance than the α, β-substituted dye.

Although the specific example (compounds I-1 to I-12 and 101-190) of the phthalocyanine dye of General formula (2) and (5) is shown below, the phthalocyanine dye used for this invention is not limited to these. .

Compound no. The structure of the phthalocyanine compound of 146-190 is shown below. m and n each represent the number of substituents.

(X _p1 is independently R ₁₁ or R ₁₂ )

The phthalocyanine dye of general formula (2) can be manufactured according to description in the said patent document. The phthalocyanine dye of general formula (5) can be manufactured according to the method mentioned above, or according to the method of Unexamined-Japanese-Patent No. 2001-226275, 2001-96610, 2001-47013, 2001-193638. Starting materials, dye intermediates and preparation routes are not limited to those cited herein.

In the ink set for ink jet of the present invention, the content of the dye of the general formula (2) in the cyan ink is preferably 0.2 to 20% by weight, more preferably 0.5 to 15% by weight.

[Dye of General Formula (3)]

The dye of the general formula (3) used in the present invention is a (heterocycle A) -N = N- (heterocycle B) in which at least one azo group is directly connected to a coupling component of an aromatic nitrogen-containing six-membered heterocycle. It has a dye structure in the form having a chromophore of. Preferably, the dye has a structure containing an aromatic amino group or a heterocyclic amino group as a crude group. Also, preferably, by removing α-hydrogen from the azo dye, the azo dye may have an increased oxidation potential. The method for increasing the oxidation potential of azo dyes is described in detail in Japanese Patent Laid-Open No. 2001-254878.

The accelerated fading rate constant for the ozone gas of the dye is preferably at most 5.0 × 10 ⁻² [hour ⁻¹ ], more preferably at most 3.0 × 10 ⁻² [hour ⁻¹ ], even more preferably 1.5 × 10 ^-2 [time ^-1 ].

The accelerated fading rate constant for the ozone gas of the dye is determined as follows: only the dye is printed on the reflective aqueous medium, and the reflection measured with the filter of status A with the color of the main spectral absorption region of the dye thus formed A part of the colored region of the image whose density is 0.90 to 1.10 is specifically selected as the initial concentration point. The initial concentration is taken as the starting concentration (= 100%). The image is faded in an ozone fading tester with an ozone concentration of 5 mg / L at all times. The time at which the concentration of the discolored sample is reduced to 80% of the initial concentration of the original sample is measured, and the reciprocal of the time [time ⁻¹ ] is obtained. Assuming that the fading concentration and the fading time follow the first-order reaction rate equation, the value is defined as the fading reaction rate constant. Therefore, the discoloration rate constant obtained by the above method is the discoloration rate constant of the region in which the dye, that is, the ink containing the tested dye, is colored. In the present invention, this is referred to as the discoloration rate constant of the ink.

The test print patch may be either a patch printed with JIS code 2223 black square, a stepped color patch of a Macbed chart, or any other step density patch capable of area measurement.

The reflection density of the printed reflective image (gradual color patch) for measurement is measured through a Status A filter using a densitometer that meets the international standard ISO5-4 (geometric conditions of reflection density).

The test chamber for accelerated fading test constant test for ozone gas is equipped with an ozone generator (for example, a high-pressure discharge method that applies AC voltage to dry air) to maintain the internal ozone concentration at 5 mg / L at all times, so that the sample is generated. The temperature exposed to the device is adjusted to 25 ° C.

The accelerated fading rate constant is an indicator of the oxidizing power of the sample in an oxidizing atmosphere, such as, for example, photochemical smog, automobile exhaust, organic vapors from painted furniture or carpets, or the environment of gases generated from a picture frame of a bright room. Specifically, ozone gas represents these oxidation atmospheres.

The magenta ink containing the dye is preferably having a λmax of 500 to 580 nm because of good color. In addition, it is preferable that the half width of both the long wave side and the short wave side of the maximum absorption wavelength of the ink is small, that is, the ink has sharp absorption. Specifically, it is described in Unexamined-Japanese-Patent No. 2002-309133. In addition, sharp light absorption of the dye is realized by introducing a methyl group at the α-position of the dye (eg, R ₃₂ in General Formula (3-A)).

In General formula (3), A <_31> represents a 5-membered heterocycle.

B ₃₁ and B ₃₂ each represent = CR ₃₁ -or -CR ₃₂ =, or one of them is a nitrogen atom, and the other is = CR ₃₁ -or -CR ₃₂ =. R ₃₅ and R ₃₆ each independently represent a hydrogen atom or a substituent. The substituent is an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group or a sulfamoyl group, and even if the hydrogen atom in each group is substituted good.

G ₃ , R ₃₁ and R ₃₂ each independently represent a hydrogen atom or a substituent. The substituent is a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, heterocyclic group Oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonyl Amino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkylthio group, arylthio group, heterocyclic thi group, alkylsulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, alkylsulfinyl group And an arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group or a sulfo group, and the hydrogen atom in each group may be substituted.

R ₃₁ and R ₃₅ or R ₃₅ and R ₃₆ may be bonded to each other to form a 5- or 6-membered ring.

The dye of General formula (3) is demonstrated in more detail.

In General formula (3), A <_31> represents a 5-membered heterocyclic group. Heteroatoms of the heterocycle include N, O and S. Preferably, the heterocycle is a nitrogen-containing 5-membered heterocycle. The heterocycle may be condensed with an aliphatic ring, an aromatic ring or any other heterocycle. Preferred examples of the heterocyclic ring of A ₃₁ are pyrazole, imidazole, thiazole, isothiazole, thiadiazole, benzothiazole, benzoxazole and benzisothiazole ring. These heterocycles may further be substituted. Especially, pyrazole, imidazole, isothiazole, thiadiazole, and benzothiazole ring of the following general formula (a)-(f) are preferable.

In General Formulas (a) to (f), R ₃₀₇ to R ₃₂₀ represent the same substituents as those described for G ₃ , R ₃₁ and R ₃₂ in General Formula (3).

In general formula (a)-(f), the pyrazole and isothiazole ring of general formula (a) and (b) are preferable; The pyrazole ring of general formula (a) is the most preferable.

In formula (3), B ₃₁ and B ₃₂ represent = CR ₃₁ -or -CR ₃₂ =, or one of them represents a nitrogen atom and the other represents = CR ₃₁ -or -CR ₃₂ = . Preferably, = CR ₃₁ -and -CR ₃₂ =.

R ₃₅ and R ₃₆ independently represent a hydrogen atom or a substituent. Examples of the substituent include aliphatic groups, aromatic groups, heterocyclic groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, alkylsulfonyl groups, arylsulfonyl groups or sulfamoyl groups. The hydrogen atom in the said group may be substituted.

R ₃₅ and R ₃₆ are each preferably a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or an alkyl or arylsulfonyl group; More preferably a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, or an alkyl or arylsulfonyl group; More preferably, they are a hydrogen atom, an aryl group, or a heterocyclic group. The hydrogen atom in the said group may be substituted. However, R ₃₅ and R ₃₆ are not simultaneously hydrogen atoms.

G ₃ , R ₃₁ and R ₃₂ each independently represent a hydrogen atom or a substituent. Examples of the substituent include a halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group and hetero Cyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbon Bonylamino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkylthio group, arylthio group, heterocyclic thi group, alkylsulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, alkylsulphi And a arylsulfinyl group, a heterocyclic sulfinyl group, a sulfamoyl group, and a sulfo group. The hydrogen atom in the said group may be substituted.

Examples of G ₃ include hydrogen atom, halogen atom, aliphatic group, aromatic group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, heterocyclic oxy group, amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group An aryloxycarbonylamino group, an alkyl or arylthio group, or a heterocyclic thi group is preferable; More preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, an amino group or an acylamino group; Most preferred is a hydrogen atom, an amino group (preferably an anilino group) or an acylamino group. The hydrogen atom in the said group may be substituted.

R ₃₁ and R ₃₂ are each preferably a hydrogen atom, an alkyl group, a halogen atom, an alkoxycarbonyl group, a carboxyl group, a carbamoyl group, a hydroxy group, an alkoxy group or a cyano group. The hydrogen atom in these groups may be substituted.

R ₃₁ and R ₃₅ or R ₃₅ and R ₃₆ may be bonded to each other to form a 5- or 6-membered ring.

When A ₃₁ is substituted, or when the substituents of R ₃₁ , R ₃₂ , R ₃₅ , R ₃₆ and G ₃ are further substituted, the substituents of the substituted group are G ₃ , R ₃₁ and R ₃₂ . The listed substituents are listed.

When the dye of the general formula (3) used in the present invention is soluble in water, any one of A ₃₁ , R ₃₁ , R ₃₂ , R ₃₅ , R ₃₆ and G ₃ further has an ionic hydrophilic group as a substituent. desirable. Examples of the ionic hydrophilic group as the substituent include a sulfo group, a carboxyl group, a phosphono group and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group and a sulfo group are preferable; More preferred are carboxyl groups and sulfo groups. The carboxyl group, phosphono group and sulfo group may form a salt. Examples of counter ions that form salts include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions) and organic cations (eg, tetramethylammonium ions, tetramethylguanidium ions, tetramethylphosphonium ions). There is.

The substituent which is a term used here is demonstrated. This term is common to both General Formula (3) and General Formula (3) and General Formula (3-A) described later.

Halogen atoms include fluorine, chlorine and bromine atoms.

Aliphatic groups include alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups, alkynyl groups, substituted alkynyl groups, aralkyl groups and substituted aralkyl groups. "Substituted" in the "substituted alkyl group" and the like means that the hydrogen atom present in the "alkyl group" or the like is substituted with the substituents listed in G ₃ , R ₃₁ and R ₃₂ .

The aliphatic group may be branched or cyclic. 1-20 are preferable and, as for carbon number of an aliphatic group, 1-16 are more preferable. As an aryl site of the said aralkyl group and a substituted aralkyl group, a phenyl or a naphthyl group is preferable, and a phenyl group is more preferable. Examples of aliphatic groups include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, 4-sulfobutyl, cyclohexyl, benzyl, 2-phenethyl, vinyl and allyl groups.

Aromatic groups include aryl groups and substituted aryl groups. As an aryl group, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. Carbon number of an aromatic group becomes like this. Preferably it is 6-20 pieces, More preferably, it is 6-16 pieces.

Examples of aromatic groups are phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl groups.

Heterocyclic groups include substituted heterocyclic groups and unsubstituted heterocyclic groups. The heterocycle may be condensed with an aliphatic ring, an aromatic or any other heterocycle. As a heterocyclic group, a 5- or 6-membered heterocyclic group is preferable. Examples of the substituent of the substituted heterocyclic group include an aliphatic group, a halogen atom, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acylamino group, a sulfamoyl group, a carbamoyl group, and an ionic hydrophilic group. Examples of heterocyclic groups include 2-pyridyl, 2-thienyl, 2-thiazolyl, 2-benzothiazolyl, 2-benzooxazolyl and 2-furyl groups.

Carbamoyl groups include substituted carbamoyl groups and unsubstituted carbamoyl groups. An example of the substituent of a substituted carbamoyl group is an alkyl group. Examples of carbamoyl groups are methylcarbamoyl and dimethylcarbamoyl groups.

The alkoxycarbonyl group includes a substituted alkoxycarbonyl group and an unsubstituted alkoxycarbonyl group. As for carbon number of an alkoxycarbonyl group, 2-20 are preferable. Examples of the substituent of the substituted alkoxycarbonyl group are ionic hydrophilic groups. Examples of alkoxycarbonyl groups are methoxycarbonyl and ethoxycarbonyl groups.

The aryloxycarbonyl group includes a substituted aryloxycarbonyl group and an unsubstituted aryloxycarbonyl group. As for carbon number of an aryloxycarbonyl group, 7-20 are preferable. Examples of the substituent of the substituted aryloxycarbonyl group include an ionic hydrophilic group. Examples of the arylcarbonyl group are phenoxycarbonyl groups.

The heterocyclic oxycarbonyl group includes a substituted heterocyclic oxycarbonyl group and an unsubstituted heterocyclic oxycarbonyl group. Examples of the heterocyclic moiety of the group include those listed in the heterocycle of the heterocyclic group. As for carbon number of a heterocyclic oxycarbonyl group, 2-20 pieces are preferable. Examples of the substituent of the substituted heterocyclic oxycarbonyl group include an ionic hydrophilic group. Examples of heterocyclic oxycarbonyl groups are 2-pyridyloxycarbonyl groups.

Acyl groups include substituted acyl groups and unsubstituted acyl groups. As for carbon number of an acyl group, 1-20 are preferable. An example of a substituent of a substituted acyl group is an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

The alkoxy group includes a substituted alkoxy group and an unsubstituted alkoxy group. As for carbon number of an alkoxy group, 1-20 are preferable. Examples of the substituent of the substituted alkoxy group include an alkoxy group, a hydroxy group and an ionic hydrophilic group. Examples of alkoxy groups include methoxy, ethoxy, isopropoxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy groups.

The aryloxy group includes a substituted aryloxy group and an unsubstituted aryloxy group. As for carbon number of an aryloxy group, 6-20 are preferable. Examples of the substituent of the substituted aryloxy group include an alkoxy group and an ionic hydrophilic group. Examples of aryloxy groups are phenoxy, p-methoxyphenoxy and o-methoxyphenoxy groups.

Heterocyclic oxy groups include substituted heterocyclic oxy groups and unsubstituted heterocyclic oxy groups. As for carbon number of heterocyclic oxy group, 2-20 pieces are preferable. Examples of the substituent of unsubstituted heterocyclic oxy group include an alkyl group, an alkoxy group and an ionic hydrophilic group. Examples of heterocyclic oxy groups include 3-pyridyloxy and 3-thienyloxy groups.

The silyloxy group is preferably one substituted with an aliphatic and / or aromatic group having 1 to 20 carbon atoms. Examples of silyloxy groups include trimethylsilyloxy and diphenylmethylsilyloxy groups.

The acyloxy group includes a substituted acyloxy group and an unsubstituted acyloxy group. As for carbon number of an acyloxy group, 1-20 are preferable. An example of a substituent of a substituted acyloxy group is an ionic hydrophilic group. Examples of acyloxy groups are acetoxy and benzoyloxy groups.

Carbamoyloxy groups include substituted carbamoyloxy groups and unsubstituted carbamoyloxy groups. An example of the substituent of a substituted carbamoyloxy group is an alkyl group. Examples of carbamoyloxy groups are N-methylcarbamoyloxy groups.

The alkoxycarbonyloxy group includes a substituted alkoxycarbonyloxy group and an unsubstituted alkoxycarbonyloxy group. As for carbon number of an alkoxycarbonyloxy group, 2-20 pieces are preferable. Examples of alkoxycarbonyloxy groups are methoxycarbonyloxy and isopropoxycarbonyloxy groups.

The aryloxycarbonyloxy group includes a substituted aryloxycarbonyloxy group and an unsubstituted aryloxycarbonyloxy group. As for carbon number of an aryloxycarbonyloxy group, 7-20 are preferable. Examples of the aryloxycarbonyloxy group are phenoxycarbonyloxy groups.

The amino group includes a substituted amino group and an unsubstituted amino group. Examples of the substituent of the substituted amino group include an alkyl group, an aryl group and a heterocyclic group. Alkyl, aryl, and heterocyclic groups may be further substituted. Examples of the alkylamino group include a substituted alkylamino group and an unsubstituted alkylamino group. As for carbon number of an alkylamino group, 1-20 are preferable. An example of a substituent of a substituted alkylamino group is an ionic hydrophilic group. Examples of the alkylamino group include methylamino group and diethylamino group.

The arylamino group includes a substituted arylamino group and an unsubstituted arylamino group. As for carbon number of an arylamino group, 6-20 are preferable. Examples of the substituent of the substituted arylamino group include a halogen atom and an ionic hydrophilic group. Examples of arylamino groups are phenylamino and 2-chlorophenylamino groups.

The heterocyclic amino group includes a substituted heterocyclic amino group and an unsubstituted heterocyclic amino group. Examples of the heterocyclic moiety of the group include those listed in the heterocycle of the heterocyclic group described above. C2-C20 of a heterocyclic amino group is preferable. Examples of the substituent of the substituted heterocyclic amino group include an alkyl group, a halogen atom and an ionic hydrophilic group.

Acylamino groups include substituted acylamino groups and unsubstituted acylamino groups. As for carbon number of an acylamino group, 2-20 are preferable. An example of a substituent of a substituted acylamino group is an ionic hydrophilic group. Examples of acylamino groups are acetylamino, propionylamino, benzoylamino, N-phenylacetylamino and 3,5-disulfobenzoylamino groups.

The ureido group includes a substituted ureido group and an unsubstituted ureido group. As for carbon number of a ureido group, 1-20 are preferable. Examples of the substituent of the substituted ureido group include an alkyl group and an aryl group. Examples of ureido groups include 3-methylureido, 3,3-dimethylureido and 3-phenylureido groups.

The sulfamoylamino group includes a substituted sulfamoylamino group and an unsubstituted sulfamoylamino group. Examples of the substituent of the substituted sulfamoylamino group include an alkyl group. Examples of sulfamoylamino groups are N, N-dipropylsulfamoylamino groups.

The alkoxycarbonylamino group includes a substituted alkoxycarbonylamino group and an unsubstituted alkoxycarbonylamino group. As for carbon number of an alkoxycarbonylamino group, 2-20 pieces are preferable. Examples of the substituent of the substituted alkoxycarbonylamino group include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group are ethoxycarbonylamino groups.

The aryloxycarbonylamino group includes a substituted aryloxycarbonylamino group and an unsubstituted aryloxycarbonylamino group. As for carbon number of an aryloxycarbonylamino group, 7-20 are preferable. An example of a substituent of a substituted aryloxycarbonylamino group is an ionic hydrophilic group. An example of an aryloxycarbonylamino group is a phenoxycarbonylamino group.

Alkylsulfonylamino and arylsulfonylamino groups include substituted alkylsulfonylamino and arylsulfonylamino groups, and unsubstituted alkylsulfonylamino groups and arylsulfonylamino groups. As for carbon number of an alkylsulfonylamino group and an arylsulfonylamino group, 1-20 are preferable. Examples of the substituent of the substituted alkylsulfonylamino group and the arylsulfonylamino group are ionic hydrophilic groups. Examples of alkylsulfonylamino and arylsulfonylamino groups are methylsulfonylamino, N-phenyl-methylsulfonylamino, phenylsulfonylamino and 3-carboxyphenylsulfonylamino groups.

The heterocyclic sulfonylamino group includes a substituted heterocyclic sulfonylamino group and an unsubstituted heterocyclic sulfonylamino group. Examples of the heterocyclic moiety of the group include those described as heterocycles of the heterocyclic group. As for carbon number of a heterocyclic sulfonylamino group, 1-12 are preferable. An example of a substituent of a substituted heterocyclic sulfonylamino group is an ionic hydrophilic group. Examples of heterocyclic sulfonylamino groups include 2-thiophenesulfonylamino and 3-pyridinesulfonylamino groups.

Alkylthio, arylthio and heterocyclic thio groups include substituted alkylthio, arylthio, and heterocyclic thio groups and unsubstituted alkylthio, arylthio and heterocyclic thio groups. Examples of the heterocyclic moiety of the group include those described as heterocycles of the heterocyclic group. As for carbon number of alkylthio, arylthio, and a heterocyclic thi group, 1-20 are preferable. Examples of the substituents of substituted alkylthio, arylthio and heterocyclic thio groups are ionic hydrophilic groups. Examples of alkylthio, arylthio and heterocyclic thio groups are methylthio, phenylthio and 2-pyridylthio groups.

Alkylsulfonyl and arylsulfonyl groups include substituted alkylsulfonyl and arylsulfonyl groups and unsubstituted alkylsulfonyl and arylsulfonyl groups. Examples of alkylsulfonyl and arylsulfonyl groups are methylsulfonyl and phenylsulfonyl groups.

Heterocyclic sulfonyl groups include substituted heterocyclic sulfonyl groups and unsubstituted heterocyclic sulfonyl groups. Examples of the heterocyclic moiety of the group include those described as heterocycles of the heterocyclic group. As for carbon number of a heterocyclic sulfonyl group, 1-20 are preferable. An example of a substituent of a substituted heterocyclic sulfonyl group is an ionic hydrophilic group. Examples of heterocyclic sulfonyl groups include 2-thienylsulfonyl and 4-pyridylsulfonyl groups.

Alkylsulfinyl and arylsulfinyl groups include substituted alkylsulfinyl and arylsulfinyl groups, and unsubstituted alkylsulfinyl and arylsulfinyl groups. Examples of alkylsulfinyl and arylsulfinyl groups are methylsulfinyl and phenylsulfinyl groups.

Heterocyclic sulfinyl groups include substituted heterocyclic sulfinyl groups and unsubstituted heterocyclic sulfinyl groups. Examples of the heterocyclic moiety of the group include those described as heterocycles of the heterocyclic group. As for carbon number of a heterocyclic sulfinyl group, 1-20 are preferable. Examples of the substituent of the substituted heterocyclic sulfinyl group include an ionic hydrophilic group. An example of a heterocyclic sulfinyl group is 4-pyridylsulfinyl group.

Sulfamoyl groups include substituted sulfamoyl groups and unsubstituted sulfamoyl groups. Examples of the substituent of the substituted sulfamoyl group include an alkyl group. Examples of sulfamoyl groups are dimethylsulfamoyl and di (2-hydroxyethyl) sulfamoyl groups.

Among the dyes of the general formula (3), those of the following general formula (3-A) are more preferable.

In formula, R <_31> , R <_32> , R <_35> and R <_36> have the same meaning as in General formula (3).

R ₃₃ and R ₃₄ each independently represent a hydrogen atom or a substituent. Examples of the substituent include aliphatic groups, aromatic groups, heterocyclic groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, alkylsulfonyl groups, arylsulfonyl groups, and sulfamoyl groups. Among them, a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkylsulfonyl group and an arylsulfonyl group are preferable; More preferred are hydrogen atoms, aromatic groups and heterocyclic groups.

Z ₃₁ represents an electron withdrawing group having a Hammet substituent constant sigma p of 0.20 or more. Z ₃₁ is preferably an electron withdrawing group having a sigma p of 0.30 or more, more preferably 0.45 or more with an electron withdrawing group, still more preferably with an electron withdrawing group of 0.60 or more, but preferably not exceeding 1.0. Preferable examples of the electron withdrawing machine are shown below. Especially, Z <_31> is a C2-C20 acyl group, a C2-C20 alkyloxycarbonyl group, a nitro group, a cyano group, a C1-C20 alkylsulfonyl group, a C6-C20 arylsulfonyl group, C1-C20 20 carbamoyl groups or halogenoalkyl groups having 1 to 20 carbon atoms are preferable; More preferably a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms or an arylsulfonyl group having 6 to 20 carbon atoms; Cyano groups are most preferred.

Z ₃₂ represents a hydrogen atom or a substituent. Examples of the substituent include aliphatic groups, aromatic groups and heterocyclic groups. Z ₃₂ is preferably an aliphatic group, more preferably an alkyl group having 1 to 6 carbon atoms.

Q represents a hydrogen atom or a substituent. Examples of the substituent include aliphatic groups, aromatic groups and heterocyclic groups. Especially, as Q, the group which consists of a nonmetallic atom necessary for forming a 5-8 membered ring is preferable. The said 5-8 membered ring may be substituted, may be a saturated ring, or an unsaturated ring may be sufficient as it. Especially, an aromatic group or a heterocyclic group is preferable. Preferred nonmetallic atoms are nitrogen, oxygen, sulfur and carbon atoms. Examples of the ring structure include benzene, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclohexene, pyridine, pyrimidine, pyrazine, pyridazine, triazine, imidazole, benzimidazole, oxazole, benzoxazole, Thiazole, benzothiazole, oxane, sulfolane and thian ring.

The hydrogen atom of each group in general formula (3-A) may be substituted. As a substituent, what was described by group G <_3> , R <_31> and R <_32> in general formula (3), and an ionic hydrophilic group are mentioned.

The Hammet substituent constant sigma p is briefly described. Hammet's law was proposed by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, and its validity has been recognized in the field so far. Substituent constants obtained by the Hammet law have two values of sigma p and sigma m, which can be seen in a number of categories. See, for example, JA Dean, Lange's Handbook of Chemistry , 12th edition, 1979 (McGraw-Hill published); And Chemical Region is shown in the jeunggan, No.122, details on pp.96 ~ 103, 1979 (Nanko- do Publishing). In the present invention, the substituents are defined or described with reference to the substituent constant? This does not mean that the substituents are limited only to those whose sigma p values are known in such literature. It goes without saying that even if the sigma p value is unknown, substituents whose substituent constants are measured according to the Hammet's law are also included in the scope of the present invention. Some of the dyes of general formula (3-A) used in the present invention are not benzene derivatives. However, [sigma] p value is used as a measure of the electronic effect of the substituent and is used for the substituent of the dye regardless of the substitution position of the substituent. In the present invention, the sigma p value is used for this effect.

Examples of electron withdrawing groups having a Hammet substituent constant? P of 0.60 or more include cyano groups, nitro groups, alkylsulfonyl groups (eg, methylsulfonyl), and arylsulfonyl groups (eg, phenylsulfonyl).

Examples of electron withdrawing groups having a Hammet substituent constant sigma p of 0.45 or more include acyl groups (e.g., acetyl), alkoxycarbonyl groups (e.g., dodecyloxycarbonyl), aryloxycarbonyl groups (e.g., m-chlorophenoxycarbonyl) ), Alkylsulfinyl groups (eg n-propylsulfinyl), arylsulfinyl groups (eg phenylsulfinyl), sulfamoyl groups (eg N-ethylsulfayl, N, N-dimethylsulfamoyl), and halogeno Alkyl groups (eg trifluoromethyl) are listed.

Examples of electron withdrawing groups having a Hammet substituent constant? P of 0.30 or more include acyloxy groups (eg, acetoxy) and carbamoyl groups (eg, N-ethylcarbamoyl, N, N-diethylcarbamoyl) in addition to the groups described above. , Halogenoalkoxy group (e.g. trifluoromethoxy), halogenoaryloxy group (e.g. pentafluorophenyloxy), sulfonyloxy group (e.g. methylsulfonyloxy), halogenoalkylthio group (e.g. di Fluoromethylthio), an aryl group (e.g., 2,4-dinitrophenyl, pentachlorophenyl) substituted with two or more electron withdrawing groups, each having a sigma p of at least 0.15, and a heterocyclic group (e.g., 2-benzooxazolyl, 2 -Benzothiazolyl, 1-phenyl-2-benzimidazolyl).

Examples of electron withdrawing groups having a sigma p of 0.20 or more include halogen atoms in addition to the aforementioned groups.

Especially preferable combination of the substituent of the azo dye of General formula (3) is mentioned later. R ₃₅ and R ₃₆ are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfonyl group or an acyl group; More preferably a hydrogen atom, an aryl group, a heterocyclic group or a sulfonyl group; Most preferred is a hydrogen atom, an aryl group or a heterocyclic group. However, R ₃₅ and R ₃₆ must not be hydrogen atoms at the same time.

As G ₃ , a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an amino group or an acylamino group is preferable, a hydrogen atom, a halogen atom, an amino group or an acylamino group is more preferable, and a hydrogen atom, an amino group or an acylamino group is most preferred.

As A ₃₁ , a pyrazole ring, an imidazole ring, an isothiazole ring, a thiadiazole ring, or a benzothiazole ring is preferable, a pyrazole ring or an isothiazole is more preferable, and a pyrazole ring is the most preferable.

As B ₃₁ and B ₃₂ , = CR ₃₁ -and -CR ₃₂ = are preferable, respectively; R ₃₁ and R ₃₂ are preferably a hydrogen atom, an alkyl group, a halogen atom, a cyano group, a carbamoyl group, a carboxyl group, a hydroxy group, an alkoxy group or an alkoxycarbonyl group, and more preferably a hydrogen atom, an alkyl group, a carboxyl group, a cyano group or a carbamoyl group. Do.

About the preferable combination of the substituent of the compound of the said General formula (3), it is preferable that 1 or more substituents are the preferable group mentioned above. More preferably, more substituents are the above-mentioned preferred group. Most preferably, all of the substituents are the preferred groups described above.

Although the specific example of the azo dye of the said General formula (3) is shown to following Table 1-Table 13, and General formula (f-1) and (f-2), this invention is not limited to this.

In the inkjet ink set of the present invention, the content of the dye of the general formula (3) in the magenta ink is preferably 0.2 to 20% by weight, more preferably 0.5 to 15% by weight. Further, the solubility of the dye in water (or dispersion degree in a stable state) at 20 ° C is preferably 5% by weight or more, more preferably 10% by weight or more.

[Dye of General Formula (4)]

The dye of the general formula (4) has a wavelength lambda max within 500 to 700 nm and a half width (Wλ, _1/2 ) of the absorption spectrum of the dilute solution of the dye normalized so that the absorbance is 1.0, 100 nm or more, preferably 120 to 500 nm, More preferably, it is 120-350 nm. This form of dye (L) is demonstrated.

The dye (L) may be used alone for black ink as long as it can realize a high quality "tight" black image by itself (no highlighting of B, G and R colors regardless of the observation light source). However, it is usually combined with other dyes that can cover areas that are hardly absorbed by the dye (L). Specifically, the dye (L) is preferably combined with a dye (S) having a main absorption (λ max is 350 ~ 500nm) in the yellow region. In addition, similarly to the above case, the black ink may be formed by combining the dye (L) with another dye.

In the present invention, the dye is preferably used alone or in combination with other dyes to produce black ink. Preferred characteristics of the black ink are 1) excellent weather resistance, and / or 2) the image does not lose black balance even after fading. In order to have the said preferable characteristic, it is preferable that a black ink satisfy | fills the following conditions.

Using the black ink, a 48-point size black square symbol of JIS code 2223 is printed, and its reflection density (D _vis ) is measured through a status A filter (visual filter). This is taken as the initial concentration of the sample. An example of a reflectometer with a status A filter is an X-Rite densitometer. In order to measure the concentration of "black" here, the measured data D _vis is taken as the standard observation reflectivity. The printed material is forcibly faded using an ozone fading tester that generates 5 ppm of ozone at all times. Measure the time (t) at which the reflection density (D _vis ) of the faded sample is reduced to 80% of the initial reflection concentration of the original sample, and the acceleration fading rate constant (k _vis ) is _expressed by the relation "0.8 = exp (-k _vis ㆍ t) ".

The speed constant (k _vis ) of the black ink in the present invention is preferably at most 5.0 × 10 ⁻² [hour ⁻¹ ], more preferably at most 3.0 × 10 ⁻² [hour ⁻¹ ], even more preferably The maximum is 1.0 × 10 ⁻² [hour ⁻¹ ].

Using black ink, a 48-point size black square symbol of JIS code 2223 was printed, and the reflection concentration of three colors C (cyan), M (magenta), and Y (yellow) other than D _{vis was determined} by the Status A filter. Measure through. The data measured in this way are taken as initial concentrations D _R , D _G and D _B. These data D _R , D _G and D _B represent the C reflection concentration through the red filter, the M reflection concentration through the green filter and the Y reflection concentration through the blue filter, respectively. The printed material is forcibly discolored in the same manner as above by using an ozone fading tester which generates 5 ppm of ozone at all times. From the time t at which the reflection concentrations D _R , D _G and D _B of the faded sample are reduced to 80% of the initial concentration of the original sample, the accelerated fading rate constant (k _R , k _G , k _B ) is derived in the same manner as above. The ratio R of the maximum value to the minimum value of the three speed constants (e.g., when k _R is the maximum value and k _G is the minimum value, R = k _R / k _G ) is preferably at most 1.2, and more Preferably it is 1.1, More preferably, it is 1.05.

In the " printed black square symbol of JIS code 2223 of 48-point size ", the image is printed in a size that completely covers the opening of the meter so as to be sufficient for density measurement.

You may manufacture black ink using dye (S) whose (lambda) max is 350-500 nm with dye (L) of the said General formula (4). The dye (S) corresponds to the dye of the general formula (4). In the black ink of the present invention, at least one of the dyes (L) is preferably a dye of the general formula (4), but more preferably at least one of the dyes (L) and (S) is a general formula (4). ), More preferably 90% by weight or more of the total dyes in the ink are dyes of the general formula (4).

In Formula (4), A ₄₁ , B ₄₁ and C ₄₁ each independently represent an aromatic or heterocyclic group which is optionally substituted, A ₄₁ and C ₄₁ are monovalent groups, and B ₄₁ is a divalent group. to be.

m is 1 or 2 and n is an integer of at least 0; Preferably m = n = 1.

Of the azo dyes of the general formula (4) (hereinafter, referred to as "azo dyes"), those of the following general formula (4-A) are preferable.

In General Formula (4-A), A ₄₁ and B ₄₁ have the same meanings as in General Formula (4). B ₁ and B ₂ each represent = CR ₄₁ -or -CR ₄₂ =, or one of them is a nitrogen atom, and the other is = CR ₄₁ -or -CR ₄₂ =.

G ₄ , R ₄₁ and R ₄₂ are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, or an acyl group , Hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (alkylamino group, arylamino group, hetero Cyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkyl or arylthio group, alkyl or Arylsulfonyl group, heterocyclic sulfonyl group, alkyl or arylsulfinyl group, heterocyclic sulfinyl group, sulfamoyl group or sulfo group. These groups may be substituted.

R ₄₅ and R ₄₆ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl or arylsulfonyl group, or a sulfamoyl group. These groups may be further substituted. However, R ₄₅ and R ₄₆ are not simultaneously hydrogen atoms.

R ₄₁ and R ₄₅ or R ₄₅ and R ₄₆ may be bonded to each other to form a 5- or 6-membered ring.

Among the azo dyes of the general formula (4-A), those of the following general formula (4-B) are more preferable.

In General Formula (4-B), R ₄₇ and R ₄₈ have the same meanings as those of R ₄₁ in General Formula (4-A).

Halogen atoms include fluorine, chlorine and bromine atoms. Aliphatic groups include alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups, alkynyl groups, substituted alkynyl groups, aralkyl groups and substituted aralkyl groups. The aliphatic group may be branched or cyclic. 1-20 are preferable and, as for carbon number of an aliphatic group, 1-16 are more preferable. As an aryl site of an aralkyl group and a substituted aralkyl group, a phenyl or a naphthyl group is preferable, and a phenyl group is more preferable. Examples of aliphatic groups include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl, cyclohexyl, benzyl, 2-phenethyl, vinyl and allyl groups are listed.

Monovalent aromatic groups include an aryl group and a substituted aryl group. As an aryl group, a phenyl group or a naphthyl group is preferable, More preferably, it is a phenyl group. Carbon number of monovalent aromatic group becomes like this. Preferably it is 6-20 pieces, More preferably, it is 6-16 pieces. Examples of monovalent aromatic groups include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and m- (3-sulfopropylamino) phenyl groups. The divalent aromatic group is different from the monovalent aromatic group but is corresponding, i.e., 2a. Examples are phenylene, p-tolylene, p-methoxyphenylene, o-chlorophenylene, m- (3-sulfopropylamino) phenylene and naphthylene groups.

Heterocyclic groups include substituted heterocyclic groups and unsubstituted heterocyclic groups. The heterocycle may be condensed with an aliphatic ring, an aromatic or any other heterocycle. As a heterocyclic group, a 5- or 6-membered heterocyclic group is preferable. Heteroatoms forming the heterocycle include N, O and S. Examples of the substituent of the substituted heterocyclic group include an aliphatic group, a halogen atom, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acylamino group, a sulfamoyl group, a carbamoyl group, and an ionic hydrophilic group. Heterocycles of monovalent and divalent heterocyclic groups include pyridine, thiophene, thiazole, benzothiazole, benzoxazole and furan ring.

Carbamoyl groups include substituted carbamoyl groups and unsubstituted carbamoyl groups. An example of the substituent of a substituted carbamoyl group is an alkyl group. Examples of carbamoyl groups are methylcarbamoyl and dimethylcarbamoyl groups.

The alkoxycarbonyl group includes a substituted alkoxycarbonyl group and an unsubstituted alkoxycarbonyl group. As for carbon number of an alkoxycarbonyl group, 2-20 are preferable. Examples of the substituent of the substituted alkoxycarbonyl group are ionic hydrophilic groups. Examples of alkoxycarbonyl groups are methoxycarbonyl and ethoxycarbonyl groups.

The aryloxycarbonyl group includes a substituted aryloxycarbonyl group and an unsubstituted aryloxycarbonyl group. As for carbon number of an aryloxycarbonyl group, 7-20 are preferable. Examples of the substituent of the substituted aryloxycarbonyl group include an ionic hydrophilic group. Examples of the alkoxycarbonyl group are phenoxycarbonyl groups.

The heterocyclic oxycarbonyl group includes a substituted heterocyclic oxycarbonyl group and an unsubstituted heterocyclic oxycarbonyl group. As for carbon number of a heterocyclic oxycarbonyl group, 2-20 pieces are preferable. An example of a substituent of a substituted heterocyclic oxycarbonyl group is an ionic hydrophilic group. Examples of heterocyclic oxycarbonyl groups are 2-pyridyloxycarbonyl groups.

Acyl groups include substituted acyl groups and unsubstituted acyl groups. As for carbon number of an acyl group, 1-20 are preferable. An example of a substituent of a substituted acyl group is an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

The alkoxy group includes a substituted alkoxy group and an unsubstituted alkoxy group. As for carbon number of an alkoxy group, 1-20 are preferable. Examples of the substituent of the substituted alkoxy group include an alkoxy group, a hydroxy group and an ionic hydrophilic group. Examples of alkoxy groups include methoxy, ethoxy, isopropoxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy groups.

The aryloxy group includes a substituted aryloxy group and an unsubstituted aryloxy group. As for carbon number of an aryloxy group, 6-20 are preferable. Examples of the substituent of the substituted aryloxy group include an alkoxy group and an ionic hydrophilic group. Examples of aryloxy groups are phenoxy, p-methoxyphenoxy and o-methoxyphenoxy groups.

Heterocyclic oxy groups include substituted heterocyclic oxy groups and unsubstituted heterocyclic oxy groups. As for carbon number of heterocyclic oxy group, 2-20 pieces are preferable. Examples of the substituent of the substituted heterocyclic oxy group include an alkyl group, an alkoxy group and an ionic hydrophilic group. Examples of heterocyclic oxy groups include 3-pyridyloxy and 3-thienyloxy groups.

The silyloxy group is preferably one substituted with an aliphatic and / or aromatic group having 1 to 20 carbon atoms. Examples of silyloxy groups include trimethylsilyloxy and diphenylmethylsilyloxy groups.

The acyloxy group includes a substituted acyloxy group and an unsubstituted acyloxy group. As for carbon number of an acyloxy group, 1-20 are preferable. An example of a substituent of a substituted acyloxy group is an ionic hydrophilic group. Examples of acyloxy groups are acetoxy and benzoyloxy groups.

Carbamoyloxy groups include substituted carbamoyloxy groups and unsubstituted carbamoyloxy groups. An example of the substituent of a substituted carbamoyloxy group is an alkyl group. Examples of carbamoyloxy groups are N-methylcarbamoyloxy groups.

The alkoxycarbonyloxy group includes a substituted alkoxycarbonyloxy group and an unsubstituted alkoxycarbonyloxy group. As for carbon number of an alkoxycarbonyloxy group, 2-20 pieces are preferable. Examples of alkoxycarbonyloxy groups are methoxycarbonyloxy and isopropoxycarbonyloxy groups.

The aryloxycarbonyloxy group includes a substituted aryloxycarbonyloxy group and an unsubstituted aryloxycarbonyloxy group. As for carbon number of an aryloxycarbonyloxy group, 7-20 are preferable. Examples of the aryloxycarbonyloxy group are phenoxycarbonyloxy groups.

The amino group includes an unsubstituted amino group and an amino group substituted with an alkyl group, an aryl group or a heterocyclic group. The substituent of alkyl, aryl, and a heterocyclic group may further be substituted. As for carbon number of an alkylamino group, 1-20 are preferable. An example of a substituent of a substituted alkylamino group is an ionic hydrophilic group. Examples of the alkylamino group include methylamino group and diethylamino group.

The arylamino group includes a substituted arylamino group and an unsubstituted arylamino group. As for carbon number of an arylamino group, 6-20 are preferable. Examples of the substituent of the substituted arylamino group include a halogen atom and an ionic hydrophilic group. Examples of arylamino groups are anilino and phenylamino and 2-chlorophenylamino groups.

The heterocyclic amino group includes a substituted heterocyclic amino group and an unsubstituted heterocyclic amino group. C2-C20 of a heterocyclic amino group is preferable. Examples of the substituent of the substituted heterocyclic amino group include an alkyl group, a halogen atom and an ionic hydrophilic group.

Acylamino groups include substituted acylamino groups and unsubstituted acylamino groups. As for carbon number of an acylamino group, 2-20 are preferable. An example of a substituent of a substituted acylamino group is an ionic hydrophilic group. Examples of acylamino groups are acetylamino, propionylamino, benzoylamino, N-phenylacetylamino and 3,5-disulfobenzoylamino groups.

The ureido group includes a substituted ureido group and an unsubstituted ureido group. As for carbon number of a ureido group, 1-20 are preferable. Examples of the substituent of the substituted ureido group include an alkyl group and an aryl group. Examples of ureido groups include 3-methylureido, 3,3-dimethylureido and 3-phenylureido groups.

The sulfamoylamino group includes a substituted sulfamoylamino group and an unsubstituted sulfamoylamino group. Examples of the substituent of the substituted sulfamoylamino group include an alkyl group. Examples of sulfamoylamino groups are N, N-dipropylsulfamoylamino groups.

The alkoxycarbonylamino group includes a substituted alkoxycarbonylamino group and an unsubstituted alkoxycarbonylamino group. As for carbon number of an alkoxycarbonylamino group, 2-20 pieces are preferable. Examples of the substituent of the substituted alkoxycarbonylamino group are ionic hydrophilic groups. Examples of the alkoxycarbonylamino group are ethoxycarbonylamino groups.

The aryloxycarbonylamino group includes a substituted aryloxycarbonylamino group and an unsubstituted aryloxycarbonylamino group. As for carbon number of an aryloxycarbonylamino group, 7-20 are preferable. An example of a substituent of a substituted aryloxycarbonylamino group is an ionic hydrophilic group. An example of an aryloxycarbonylamino group is a phenoxycarbonylamino group.

Alkylsulfonylamino and arylsulfonylamino groups include substituted alkylsulfonylamino groups and arylsulfonylamino groups, and unsubstituted alkylsulfonylamino groups and arylsulfonylamino groups. As for carbon number of the said alkylsulfonylamino group and the arylsulfonylamino group, 1-20 are preferable. Examples of the substituent of the substituted alkylsulfonylamino group and the arylsulfonylamino group are ionic hydrophilic groups. Examples of the alkylsulfonylamino and arylsulfonylamino groups include methylsulfonylamino, N-phenyl-methylsulfonylamino, phenylsulfonylamino and 3-carboxyphenylsulfonylamino groups.

The heterocyclic sulfonylamino group includes a substituted heterocyclic sulfonylamino group and an unsubstituted heterocyclic sulfonylamino group. As for carbon number of the said heterocyclic sulfonylamino group, 1-12 are preferable. An example of a substituent of a substituted heterocyclic sulfonylamino group is an ionic hydrophilic group. Examples of heterocyclic sulfonylamino groups include 2-thiophenesulfonylamino and 3-pyridinesulfonylamino groups.

Heterocyclic sulfonyl groups include substituted heterocyclic sulfonyl groups and unsubstituted heterocyclic sulfonyl groups. As for carbon number of the said heterocyclic sulfonyl group, 1-20 are preferable. An example of a substituent of a substituted heterocyclic sulfonyl group is an ionic hydrophilic group. Examples of heterocyclic sulfonyl groups include 2-thiophenesulfonyl and 3-pyridinesulfonyl groups.

Heterocyclic sulfinyl groups include substituted heterocyclic sulfinyl groups and unsubstituted heterocyclic sulfinyl groups. As for carbon number of the said heterocyclic sulfinyl group, 1-20 are preferable. Examples of the substituent of the substituted heterocyclic sulfinyl group include an ionic hydrophilic group. An example of a heterocyclic sulfinyl group is a 4-pyridine sulfinyl group.

Alkylthio, arylthio and heterocyclic thio groups include substituted alkylthio, arylthio and heterocyclic thio groups and unsubstituted alkylthio, arylthio and heterocyclic thio groups. As for carbon number of the said alkylthio, an arylthio, and a heterocyclic thi group, 1-20 pieces are preferable. Examples of the substituents of substituted alkylthio, arylthio and heterocyclic thio groups are ionic hydrophilic groups. Examples of alkylthio, arylthio and heterocyclic thio groups are methylthio, phenylthio and 2-pyridylthio groups.

Alkylsulfonyl and arylsulfonyl groups include substituted alkylsulfonyl and arylsulfonyl groups, and unsubstituted alkylsulfonyl and arylsulfonyl groups. Examples of alkylsulfonyl and arylsulfonyl groups are methylsulfonyl and phenylsulfonyl groups.

Alkylsulfinyl and arylsulfinyl groups include substituted alkylsulfinyl and arylsulfinyl groups, and unsubstituted alkylsulfinyl and arylsulfinyl groups. Examples of alkylsulfinyl and arylsulfinyl groups are methylsulfinyl and phenylsulfinyl groups.

Sulfamoyl groups include substituted sulfamoyl groups and unsubstituted sulfamoyl groups. Examples of the substituent of the substituted sulfamoyl group include an alkyl group. Examples of sulfamoyl groups are dimethylsulfamoyl and di (2-hydroxyethyl) sulfamoyl groups.

General formula (4), (4-A), and (4-B) are further demonstrated.

In the following description, those described above for the groups and substituents apply.

In formula (4), A ₄₁ , B ₄₁ and C ₄₁ are each independently an aromatic group substituted as necessary (A ₄₁ and C ₄₁ are each monovalent aromatic groups such as aryl groups; B ₄₁ is aryl Divalent aromatic groups such as a benzene group) or a heterocyclic group (A ₄₁ and C ₄₁ are each a monovalent heterocyclic group; B ₄₁ is a divalent heterocyclic group) which is optionally substituted. Examples of the aromatic ring include benzene and naphthalene ring; Heteroatoms forming the heterocycle include N, O and S. The heterocycle may be condensed with an aliphatic ring, an aromatic ring or any other heterocycle.

The substituent may be an aryl azo group or a heterocyclic azo group.

At least one of A ₄₁ , B ₄₁ and C ₄₁ is preferably a heterocyclic group, and more preferably two or more of A ₄₁ , B ₄₁ and C ₄₁ are heterocyclic groups. A ₄₁ , B ₄₁ and C ₄₁ may all be heterocyclic groups.

As the heterocyclic group for C ₄₁ , an aromatic nitrogen-containing six-membered heterocyclic group of the following general formula (4-C) is preferable. When C ₄₁ is an aromatic nitrogen-containing six-membered heterocyclic group of formula (4-C), formula (4) corresponds to formula (4-A).

In formula (4-C), B ₁ and B ₂ each represent = CR ₄₁ -or -CR ₄₂ =, or one of them is a nitrogen atom, and the other is = CR ₄₁ -or -CR ₄₂ = Preferably = CR ₄₁ -or -CR ₄₂ =.

R ₄₅ and R ₄₆ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl or arylsulfonyl group, or sulfamoyl group. These groups may be further substituted. R ₄₅ and R ₄₆ are preferably a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or an alkyl or arylsulfonyl group, respectively. More preferably a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, or an alkyl or arylsulfonyl group; Most preferably, they are a hydrogen atom, an aryl group, or a heterocyclic group. The group may be further substituted. However, R ₄₅ and R ₄₆ are not simultaneously hydrogen atoms.

G ₄ , R ₄₁ and R ₄₂ are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, or an acyl group , Hydroxy group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (alkylamino, arylamino group, hetero Cyclic amino group), acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, heterocyclic sulfonylamino group, nitro group, alkyl or arylthio group, heterocyclic group Thio group, alkyl or arylsulfonyl group, heterocyclic sulfonyl group, alkyl or arylsulfinyl group, heterocyclic sulfinyl group, sulfamoyl group or sulfo group Out the other, each group further may be substituted.

Substituents for G ₄ include hydrogen atom, halogen atom, aliphatic group, aromatic group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, heterocyclic oxy group, amino group (including alkylamino group, arylamino group and heterocyclic amino group), An acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylthio group, or heterocyclic thio group is preferable; More preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, an amino group (alkylamino, arylamino, heterocyclic amino) or an acylamino group; Most preferred is a hydrogen atom, an anilino group or an acylamino group. These groups may be further substituted.

As the substituent of R ₄₁ and R ₄₂ , a hydrogen atom, an alkyl group, a halogen atom, an alkoxycarbonyl group, a carboxyl group, a carbamoyl group, a hydroxy group, an alkoxy group or a cyano group is preferable. These groups may be further substituted.

R ₄₁ and R ₄₅ or R ₄₅ and R ₄₆ may be bonded to each other to form a 5- or 6-membered ring.

Substituents for the substituted groups of A ₄₁ , R ₄₁ , R ₄₂ , R ₄₅ , R ₄₆ and G ₄ include those mentioned above as groups of G ₄ , R ₄₁ and R ₄₂ . Among them, preferably a dye having an _{A 41, R 41, R 42} , R 45, the ionic hydrophilic group on any position of R ₄₆ and G _4.

As an ionic hydrophilic group as a substituent, a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group are mentioned, for example. A carboxyl group, a phosphono group, or a sulfo group is preferable, and a carboxyl group or a sulfo group is more preferable. The carboxyl group, phosphono group and sulfo group may form a salt. Examples of counter ions that form salts include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions), organic cations (eg, tetramethylammonium ions, tetramethylguanidium ions, tetramethylphosphonium) Ions). Lithium ion is preferable as the counter ion.

When B ₄₁ has a ring structure, a thiophene, thiazole, imidazole, benzimidazole and thienothiazole ring are preferable as the hetoro ring. These heterocyclic groups may be further substituted. Especially, the thiophene, thiazole, imidazole, benzimidazole, and thienothiazole ring of the following general formula (a)-(e) are especially preferable. When B ₄₁ is a thiophene ring (a) and C ₄₁ has a structure of general formula (4-C), general formula (4) corresponds to general formula (4-B).

In General Formulas (a) to (e), R ₄₀₉ to R ₄₁₇ have the same meanings as the substituents of G ₄ , R ₄₁ and R ₄₂ in General Formula (4-A).

More preferably used in the present invention is to have a structure of the general formula (4-D).

In general formula (4-D), Z <_4> represents the electron withdrawing group whose Hammet substituent constant (sigma) p is 0.20 or more. Z ₄ is preferably an electron withdrawing group having a sigma p of 0.30 or more, more preferably 0.45 or more with an electron withdrawing group, still more preferably with 0.60 or more with an electron withdrawing group, but preferably not exceeding 1.0. Preferable examples of the electron withdrawing machine are shown below. Among these, Z ₄ is 2 to 20 carbon atoms of the acyl group, having from 2 to 20 carbon atoms alkyloxycarbonyl group, a nitro group, a cyano group, C 1 -C 20 alkylsulfonyl, C 6 - 20 arylsulfonyl group, C 1 -C 20 carbamoyl groups or halogenoalkyl groups having 1 to 20 carbon atoms are preferable; More preferably a cyano group, an alkylsulfonyl group having 1 to 20 carbon atoms or an arylsulfonyl group having 6 to 20 carbon atoms; Cyano groups are most preferred.

R ₄₁ , R ₄₂ , R ₄₅ and R ₄₆ in General Formula (4-D) have the same meanings as in General Formula (4-A). R ₄₃ and R ₄₄ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkyl or arylsulfonyl group, or a sulfamoyl group; Preferably a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, or an alkyl or arylsulfonyl group; More preferably, they represent a hydrogen atom, an aromatic group, or a heterocyclic group.

The group in general formula (4-D) may further be substituted. Examples of the substituent include those described above as the group of G ₄ , R ₄₁ and R _{42 in} the general formula (4-A) and an ionic hydrophilic group.

In the present invention, the substituents are defined or described with reference to the substituent constant? It means that the substituent is limited only to those whose sigma p values are known in the above documents. It goes without saying that even if the sigma p value is unknown, substituents whose substituent constants are measured according to the Hammet's law are also included in the scope of the present invention. Some of the dyes of the general formulas (4), (4-A), (4-B), (4-C) and (4-D) used in the present invention are not benzene derivatives. However, as a measure of the electronic effect of the substituent, the sigma p value is referred to the substituent of the dye regardless of the substitution position of the substituent. In the present invention, the sigma p value is used for this effect.

Examples of electron withdrawing groups having a Hammet substituent constant? P of 0.60 or more include cyano groups, nitro groups, alkylsulfonyl groups (eg, methylsulfonyl) and arylsulfonyl groups (eg, phenylsulfonyl).

Examples of electron withdrawing groups having a Hammet substituent constant sigma p of 0.45 or more include acyl groups (e.g., acetyl), alkoxycarbonyl groups (e.g., dodecyloxycarbonyl), aryloxycarbonyl groups (e.g., m-chlorophenoxycarbonyl) ), Alkylsulfinyl groups (eg n-propylsulfinyl), arylsulfinyl groups (eg phenylsulfinyl), sulfamoyl groups (eg N-ethylsulfayl, N, N-dimethylsulfamoyl), and halogeno Alkyl groups (eg trifluoromethyl) are listed.

Examples of electron withdrawing groups having a Hammet substituent constant? P of 0.30 or more include acyloxy groups (eg, acetoxy) and carbamoyl groups (eg, N-ethylcarbamoyl, N, N-diethylcarbamoyl) in addition to the groups described above. , Halogenoalkoxy group (e.g. trifluoromethoxy), halogenoaryloxy group (e.g. pentafluorophenyloxy), sulfonyloxy group (e.g. methylsulfonyloxy), halogenoalkylthio group (e.g. di Fluoromethylthio), an aryl group (e.g., 2,4-dinitrophenyl, pentachlorophenyl) substituted with two or more electron withdrawing groups, each having a sigma p of at least 0.15, and a heterocyclic group (e.g., 2-benzooxazolyl, 2 -Benzothiazolyl, 1-phenyl-2-benzimidazolyl).

Examples of electron withdrawing groups having a sigma p of 0.20 or more include halogen atoms in addition to the aforementioned groups.

The combination of the especially preferable substituent of the azo dye of general formula (4-B) is mentioned later. R ₄₅ and R ₄₆ are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfonyl group or an acyl group; More preferably a hydrogen atom, an aryl group, a heterocyclic group or a sulfonyl group; Most preferred is a hydrogen atom, an aryl group or a heterocyclic group. However, R ₄₅ and R ₄₆ are not simultaneously hydrogen atoms.

As G _{4, a} hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an amino group or an acylamino group is preferable, a hydrogen atom, a halogen atom, an amino group or an acylamino group is more preferable, and a hydrogen atom, an amino group or an acylamino group is most preferred.

As A _{41, a} pyrazole ring, an imidazole ring, an isothiazole ring, a thiadiazole ring or a benzothiazole ring is preferable, a pyrazole ring or an isothiazole is more preferable, and a pyrazole ring is most preferable.

In addition, B ₁ and B ₂ are each preferably = CR ₄₁ -or -CR ₄₂ =; R ₄₁ and R ₄₂ are preferably a hydrogen atom, an alkyl group, a halogen atom, a cyano group, a carbamoyl group, a carboxyl group, a hydroxy group, an alkoxy group or an alkoxycarbonyl group, and more preferably a hydrogen atom, an alkyl group, a carboxyl group, a cyano group or a carbamoyl group. Do.

About the combination of the preferable substituent of the said azo dye, it is preferable that 1 or more substituents are the preferable group mentioned above. More preferably, more substituents are the above-mentioned preferred group. Most preferably, all of the substituents are the preferred groups described above.

Although the specific example of the azo dye which can be used for this invention is shown below, this invention is not limited to this. In the following examples, a carboxyl group, a phosphono group, and a sulfo group may form a salt. Examples of counter ions that form salts include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions) and organic cations (eg, tetramethylammonium ions, tetramethylguanidium ions, tetramethylphosphonium ions). There is). As the counter ion, lithium ion is preferable.

Azo dyes of the general formulas (4), (4-A), (4-B) and (4-D) can be prepared through the coupling reaction of the diazo component with the coupler. For example, the method of Unexamined-Japanese-Patent No. 2002-113460 can be referred.

In the black ink, as the dye (S) having a λmax of 350 nm to 500 nm, yellow dyes and yellow pigments that retreat other than the above-mentioned dyes of the general formulas (1) and (4) are preferable. In the black ink, these dyes and pigments may be used together, or may be used independently in another system.

Content of the dye of General formula (4) in the black ink of this invention becomes like this. Preferably it is 0.2-20 weight%, More preferably, it is 0.5-15 weight%.

Other examples of dyes that can be used in the present invention in addition to those described above are described below. The dyes may be used alone or in combination with others in order to adjust the color tone. In the present invention, a full color image may be formed by combining a plurality of inks using a plurality of dyes in an ink set.

Yellow dyes include, for example, aryl or heterarylazo dyes having phenol, naphthol, aniline, pyrazolone, pyridone or cleaved active methylene compounds as coupling components; Azomethine dyes having a cleaved active methylene compound as a coupling component; Methine dyes such as benzylidene dye and monomethine-oxonol dye; Quinone dyes such as naphthoquinone dyes and anthraquinone dyes. Other dye species include quinophthalone dyes, nitro-nitroso dyes, acridine dyes, and acridinone dyes. These dyes may only be yellow after part of the chromophore dissociates. In this case, the counter cation may be an inorganic cation such as an alkali metal or an ammonium ion, or an organic cation such as a pyridinium or a quaternary ammonium cation, or may be a polymer cation having any of these as a partial structure.

Magenta dyes include, for example, aryl or hetaryl azo dyes having phenol, naphthol or aniline as coupling components; Azomethine dyes having pyrazolone or pyrazolotriazole as coupling components; Methine dyes such as arylidene dyes, styryl dyes, merocyanine dyes, and oxonol dyes; Carbonium dyes such as diphenylmethane dye, triphenylmethane dye, and xanthene dyes; Quinone dyes such as naphthoquinone dye, anthraquinone dye, and anthrapyridone dye; And condensed polycyclic dyes such as dioxazine dyes. These dyes may only have magenta after part of the chromophore dissociates. In this case, the counter cation may be an inorganic cation such as an alkali metal or an ammonium ion, or an organic cation such as a pyridinium or a quaternary ammonium cation, or may be a polymer cation having any of these as a partial structure.

As a cyan dye, For example, Azomethine dye, such as an indanilline dye and an indophenol dye; Polymethine, such as cyanine dye, oxonol dye, merocyanine dye; Carbonium dyes such as diphenylmethane dye, triphenylmethane dye, and xanthene dyes; Phthalocyanine dyes; Anthraquinone dyes; Aryl or heterarylazo dyes with phenol, naphthol or aniline as coupling components; And indigo and thioindigo dyes. These dyes may only exist cyan after part of the chromophore dissociates. In this case, the counter cation may be an inorganic cation such as an alkali metal or an ammonium ion, or an organic cation such as a pyridinium or a quaternary ammonium cation, or may be a polymer cation having any of these as a partial structure.

In addition, water-soluble dyes such as direct dyes, acid dyes, food dyes, basic dyes and reactive dyes may be used. Among them, the following are preferable:

C.I. Direct Red 2, 4, 9, 23, 26, 31, 39, 62, 63, 72, 75, 76, 79, 80, 81, 83, 84, 89, 92, 95, 111, 173, 184, 207, 211, 212, 214, 218, 21, 223, 224, 225, 226, 227, 232, 233, 240, 241, 242, 243, 247;

C.I. Direct Violet 7, VII, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 101;

C.I. Direct Yellow ８, ９, 11, 12, 27, 28, 29, 33, 35, 39, 41, 44, 50, 53, 58, 59, 68, 86, 87, 93, 95, 96, 98, 100, 106, 108, 109, 110, 130, 132, 142, 144, 161, 163;

C.I. Direct Blue 1, 10, 15, 22, 25, 55, 67, 68, 71, 76, 77, 78, 80, 84, 86, 87, 90, 98, 106, 108, 109, 151, 156, 158, 159, 160, 168, 189, 192, 193, 194, 199, 200, 201, 202, 203, 207, 211, 213, 214, 218, 225, 229, 236, 237, 244, 248, 249, 251, 252, 264, 270, 280, 288, 289, 291;

C.I. Direct Black ９, 17, 19, 22, 32, 51, 56, 62, 69, 77, 80, 91, 94, 97, 108, 112, 113, 114, 117, 118, 121, 122, 125, 132, 146, 154, 166, 168, 173, 199;

C.I. Acid Red 35, 42, 52, 57, 62, 80, 82, 111, 114, 118, 119, 127, 128, 131, 143, 151, 154, 158, 249, 254, 257, 261, 263, 266, 289, 299, 301, 305, 336, 337, 361, 396, 397;

C.I. Acid Violet 5, 34, 43, 47, 48, 90, 103, 126;

C.I. Acid Yellow 17, 19, 23, 25, 39, 40, 42, 44, 49, 50, 61, 64, 76, 79, 110, 127, 135, 143, 151, 159, 169, 174, 190, 195, 196, 197, 199, 218, 219, 222, 227;

C.I. Acid Blue 9, 25, 40, 41, 62, 72, 76, 78, 80, 82, 92, 106, 112, 113, 120, 127: 1, 129, 138, 143, 175, 181, 205, 207, 220, 221, 230, 232, 247, 258, 260, 264, 271, 277, 278, 279, 280, 288, 290, 326;

C.I. Acid Black 7, 24, 29, 48, 52: 1, 172;

C.I. Reactive Red 3, 13, 17, 19, 21, 22, 23, 24, 29, 35, 37, 40, 41, 43, 45, 49, 55;

C.I. Reactive Violet 1, 3, 4, 5, 6, 7, 8, 9, 16, 17, 22, 23, 24, 26, 27, 33, 34;

C.I. Reactive Yellow 2, 3, 13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42;

C.I. Reactive Blue 2, 3, 5, 8, 10, 13, 14, 15, 17, 18, 19, 21, 25, 26, 27, 28, 29, 38;

C.I. Reactive Black 4, 5, 8, 14, 21, 23, 26, 31, 32, 34;

C.I. Basic Red 12, 13, 14, 15, 18, 22, 23, 24, 25, 27, 29, 35, 36, 38, 39, 45, 46;

C.I. Basic Violet 1, 2, 3, 7, 10, 15, 16, 20, 21, 25, 27, 28, 35, 37, 39, 40, 48;

C.I. Basic Yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 39, 40;

C.I. Basic Blue 1, 3, 5, 7, 9, 22, 26, 41, 45, 46, 47, 54, 57, 60, 62, 65, 66, 69, 71;

C.I. Basic Black 8.

In the ink of the present invention, a pigment and a dye may be used in combination.

Pigments which can be used in the ink of the present invention include those commercially available and known ones described in various other documents. Literature includes, for example, Color Index (in The Society of Dyers and Colorists); New edition of the Pigment Handbook (ed. Japan Institute of Pigment Technology, 1989); Latest Pigment Application Technology (CMC Publishing, 1986); Printing Ink Technology (CMC Publishing, 1984); Industrial Organic Pigments (VCH Verlagsgesellschaft, 1993) by W. Herbst & K. Hunger. Specifically, organic pigments include azo pigments (azo-lake pigments, insoluble azo pigments, condensed azo pigments, chelate-azo pigments), polycyclic pigments (phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, indigo pigments, Quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, dyed lake pigments (lake pigments of acidic or basic dyes) and azine pigments; As an inorganic pigment, Yellow pigments, such as CI Pigment Yellow 34, 37, 42, 53; Red pigments such as CI Pigment Red 101 and 108; Blue pigments such as CI Pigment Blue 27, 29, 17: 1; Black pigments such as CI Pigment Black 7, magnetite; And white pigments such as CI Pigment White 4, 6, 18, 21 and the like.

Preferred pigments for color image formation include blue or cyan pigments such as phthalocyanine pigments, anthraquinone-based indanthrone pigments (eg, C.I. Pigment Blue 60), and dyed lake pigments such as triarylcarbonium pigments. Especially preferred are phthalocyanine pigments, and preferred examples thereof include C.I. Copper phthalocyanine such as Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 6; Aluminum phthalocyanine pigments such as monochloro or low chloro-copper phthalocyanine and those described in EP 860475; Metal-free phthalocyanine, C.I. Pigment Blue 16; And phthalocyanines having a central metal atom of Zn, Ni or Ti. Most preferred is C.I. Most preferred are Pigment Blue 15: 3, 15: 4 and aluminum phthalocyanine.

Red to violet pigments include azo pigments (preferably CI Pigment Red 3, 5, 11, 22, 38, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 52: 1, 53 : 1, 57: 1, 63: 2, 144, 146, 184; more preferably CI Pigment Red 57: 1, 146, 184); Quinacridone pigments (preferably C.I. Pigment Red 122, 192, 202, 207, 209, C. I. Pigment Violet 19, 42; more preferably C.I. Pigment Red 122); Dyeing lake pigments such as triarylcarbonium pigments (preferably xanthene type C.I. Pigment Red 81: 1, C.I. Pigment Violet 1, 2, 3, 27, 39); Dioxazine pigments (eg, C.I. Pigment Violet 23, 37); Diketopyrrolopyrrole pigments (eg, C.I. Pigment Red 254); Perylene pigments (eg, C.I. Pigment Violet 29); Anthraquinone pigments (eg C.I. Pigment Violet 5: 1, 31, 33), thioindigo pigments (eg C.I. Pigment Red 38, 88).

Examples of yellow pigments include azo pigments (preferably monoazo pigments such as CI Pigment Yellow 1, 3, 74, 98; diazo pigments such as CI Pigment Yellow 12, 13, 14, 16, 17, 83; CI Pigment Yellow 93). General azo pigments such as 94, 95, 128, 155, etc .; benzimidazolone pigments such as CI Pigment Yellow 120, 151, 154, 156, 180; more preferably, no benzidine compound is used as a starting material thereof. ; Isoindolin or isoindolinone pigments (preferably C.I. Pigment Yellow 109, 110, 137, 139); Quinophthalone pigments (preferably C.I. Pigment Yellow 138); Flavantrone pigments (eg, C.I. Pigment Yellow 24) are listed.

Black pigments include inorganic pigments (preferably carbon black, magnetite) and aniline black.

In addition to the above, an orange pigment (eg C.I. Pigment Orange 13, 16) and a green pigment (C.I. Pigment Green 7) may be used.

The pigment which can be used for the ink of this invention may be the above-mentioned nude pigment, or may be surface-treated. As the surface treatment method, the pigment may be coated with a resin or wax, or a surfactant may be attached to the pigment, or a reactive substance (for example, a radical from a silane coupling agent, an epoxy compound, a polyisocyanate or a diazonium salt) may be pigmented. It may be bonded to the surface. These are described, for example, in the following documents and patent publications.

(1) Properties and Applications of Metal Soap, published by Miyuki,

(2) Printing Ink (CMC Publishing, 1984),

(3) Latest Pigment Application Technology (CMC Publishing, 1986)

(4) United States Patents 5,554,739 and 5,571,311

(5) Japanese Patent Application Laid-open No. Hei 9-151342, Hei 10-140065, Hei 10-292143 and Hei 11-166145

In particular, self-dispersible pigments prepared by reacting diazonium salts with carbon black as in the US patent of (4) and encapsulating pigments prepared by the method described in Japanese Patent Publication (5) are excessive dispersants in the ink. It is effective because it is stably dispersed without using.

In the present invention, the pigment may be dispersed using a dispersant. Depending on the pigment used, various known pigments can be used. For example, a surfactant type small molecule dispersant or a polymer type dispersant may be used. Examples of dispersants usable here include those described in Japanese Patent Laid-Open No. 3-69949 and European Patent No. 549486. When using a dispersing agent, you may add the pigment derivative called synergy in order to promote the adsorption of the dispersing agent by a pigment.

The particle size of the pigment which can be used in the ink of the present invention is preferably 0.01 to 10 mu m, more preferably 0.05 to 1 mu m with respect to the size of the dispersed particles.

In dispersion of a pigment, the well-known technique normally used at the time of ink manufacture or toner manufacture can be used. Dispersers include horizontal or vertical agitator mills, attritors, colloid mills, ball mills, three-roll mills, pearl mills, super mills, impellers, dispersers, KD mills, dynatrons, and pressure kneaders. Any may be sufficient. These are described in detail in Latest Pigment Application Technology (CMC Publishing, 1986).

As a water-soluble dye used for this invention, the magenta dye of Unexamined-Japanese-Patent No. 2002-371214; Phthalocyanine dyes disclosed in Japanese Patent Laid-Open No. 2002-309118; And the water-soluble dyes described in Japanese Patent Application Laid-Open Nos. 2003-12952 and 2003-12956.

The ink of the present invention may be prepared by dissolving or dispersing one or more dyes as described above in a medium, water and / or water miscible organic solvents, and preferably surfactants. Ink in this invention means containing dye, water, and / or water-miscible organic solvent, and additives, such as a moisturizer, a stabilizer, a preservative, as needed.

The water-miscible organic solvent used in the present invention is a substance having functions such as drying inhibitors, penetration accelerators, and humectants in inkjet recording in the field, and particularly, is a high boiling water-miscible organic solvent. For example, alcohols (e.g., methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyhydric alcohols (e.g., ethylene glycol, di Ethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (e.g., ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tri Ethylene Glycol Monomethyl Ether, Ethylene Glycol Diacetate, Ethylene Glycol Methyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monofetyl ether), amines (e.g., ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldi Ethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (e.g. formamide, N, N-dimethylformamide) , N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1, 3-dimethyl-2-imidazolidinone, acetonitrile, acetone). You may use combining 2 or more types of these water-miscible organic solvents.

Among these, alcohol solvents are particularly preferable.

The total amount of the water-miscible organic solvent in the ink is preferably 5 to 60% by weight, more preferably 10 to 45% by weight.

When the dye is soluble in water, it is preferable to dissolve it in water at the time of manufacturing the ink of the present invention. Next, various solvents and additives are added, dissolved and mixed to obtain a uniform ink composition.

As a dissolution method of the said component, various methods, such as stirring, ultrasonic irradiation, or shake, can be used, for example. Particularly preferred method is a method of stirring the above components. When stirring the said component, various methods known in the art can be used. For example, it can stir by the method of agitation, inversion azimuth, shear force stirring using a dissolver, and the like. In addition, the magnetic stirring method which uses the shearing force with respect to the bottom of a container using a magnetic stirrer here is used preferably.

The ink of the present invention may contain a surfactant effective for adjusting the liquid properties of the ink, improving the ejection stability of the ink, improving the water resistance of the image formed with the ink, and preventing the ink on the printed matter from bleeding.

As said surfactant, Anionic surfactant, such as sodium dodecyl sulfate, sodium dodecyloxy sulfonate, sodium alkylbenzene sulfonate; Cationic surfactants such as cetylpyridinium chloride, trimethylceltylammonium chloride and tetrabutylammonium chloride; And nonionic surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene naphthyl ether, polyoxyethylene octylphenyl ether and the like. Especially preferred are nonionic surfactants.

Content of surfactant of ink is 0.001-20 weight%, Preferably it is 0.005-10 weight%, More preferably, it is 0.01-5 weight%.

When the dye is an oil-soluble dye, the ink of the present invention may be prepared by dissolving in a high boiling organic solvent and then emulsifying and dispersing in an aqueous medium.

The boiling point of the high boiling point organic solvent used for this invention is 150 degreeC or more, Preferably it is 170 degreeC or more.

For example, the solvent may include phthalates such as dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, and bis (2,4-di-tert-amylphenyl) isophthalate. , Bis (1,1-diethylpropyl) phthalate), phosphoric acid or phosphone esters (e.g. diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, dioctylbutyl phosphate, tri Cyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecyl phosphate, di-2-ethylhexylphenyl phosphate), benzoates (e.g. 2-ethylhexylbenzoate, 2,4-dichlorobenzoate, dodecylbenzo) Ate, 2-ethylhexyl p-hydroxybenzoate), amides (eg, N, N-diethyldodecanamide, N, N-diethyllaurylamide), alcohols or phenols (eg, isostearyl alcohol , 2,4-di-tert-amylphenol, aliphatic esters (e.g., dibutoxyethyl succinate, di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl Azelate, isostearyl lactate, trioctyl citrate), aniline derivatives (e.g., N, N-dibutyl-2-butoxy-5-tert-octylaniline), chloroparaffins (e.g., chlorine content 10 ~ 80% paraffins), trimethates (e.g. tributyl trimethate), dodecylbenzene, diisopropylnaphthalane, phenols (e.g., 2,4-di-tert-amylphenol, 4- Dodecyloxyphenol, 4-dodecyloxycarbonylphenol, 4- (4-dodecyloxyphenylsulfonyl) phenol), carboxylic acids (eg 2- (2,4-di-tert-amylphenoxybutyric acid) , 2-ethoxyoctane-decanoic acid), alkyl phosphates (e.g., di-2 (ethylhexyl) phosphate, diphenyl phosphate) and the like. From 0.01 to 3 times by weight, preferably about soluble dye it may be used 0.01 to 1.0 times.

High boiling point organic solvents may be used alone or in combination (e.g., tricresyl phosphate and dibutyl phthalate; trioctyl phosphate and di (2-ethylhexyl) sebacate; dibutyl phthalate and poly (Nt-butylacrylic) Amide)).

In addition to the above, examples of the high-boiling organic solvents and / or methods for preparing these high-boiling organic solvents that can be used in the present invention include, for example, US Pat. Nos. 2,322,027, 2,533,514, 2,772,163, 2,835,579, 3,594,171, 3,676,137, 3,689,271, 3,700,454, 3,748,141, 3,764,336, 3,765,897, 3,912,515, 3,936,303, 4,004,928, 4,080,209, 802,4,127,413 No. 4,207,393, 4,220,711, 4,239,851, 4,278,757, 4,353,979, 4,363,873, 4,430,421, 4,430,422, 4,464,464, 4,483,918, 4,540,606,4,540,657,4,540,657 4,728,599, 4,745,049, 4,935,321 and 5,013,639 publications; EP 276,319A, 286,253A, 289,820A, 309,158A, 309,159A, 309,160A, 509,311A, 510,576A; East German Patents 147,009, 157,147, 159,573, and 225,240A; British Patent No. 2,091,124A, Japanese Patent Publication No. 48-47335, Small 50-26530, Small 51-25133, Small 51-26036, Small 51-27921, Small 51-27922, Small 51-149028 No. 52-46816, SO 53-1520, SO 53-1521, SO 53-15127, SO 53-146622, SO 54-91325, SO 54-106228, SO 54-118246, So 55-59464, So 56-64333, So 56-81836, So 59-204041, So 61-84641, So 62-118345, So 62-247364, So 63-167357, So 63 -214744, S.63-301941, S.64-9452, S.64-9454, S.64-68745, Japanese Patent Application Laid-Open No. H01- 101543, S.1-102454, S.2-792, Hei 2-4239, Hei 2-43541, Hei 4-29237, Hei 4-30165, Hei 4-232946 and Hei 4-346338.

The usage-amount of a high boiling point organic solvent is 0.01 to 3 times by weight with respect to oil-soluble dye, Preferably it is 0.01 to 1.0 times.

In the present invention, the oil-soluble dye and the high boiling point organic solvent are emulsified and dispersed in an aqueous medium. In order to further emulsify, an organic solvent having a low boiling point may be used. Low boiling organic solvents have a boiling point of about 30 ~ 150 ℃ at normal pressure. Preferred examples thereof include esters (e.g. ethyl acetate, butyl acetate, ethyl propionate, β-ethoxyethyl acetate, methyl cellosolve acetate), alcohols (e.g. isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol ), Ketones (eg methyl isobutyl ketone, methylethyl ketone, cyclohexanone), amides (eg dimethylformamide, N-methylpyrrolidone), ethers (eg tetrahydrofuran, dioxane) Enumerated, but not limited to this.

The emulsion dispersion is as follows: the oil is prepared by dissolving the dye in a high boiling organic solvent alone or in a mixture with its low boiling organic solvent, and dispersing it in an aqueous phase containing mainly water to form minute oily residues. . In this method, additives such as surfactants, humectants, dye stabilizers, emulsion stabilizers, preservatives and antifungal agents may be added to any or all of the aqueous phase and the oil phase as necessary.

In emulsification, an oil phase is usually added to an aqueous phase. However, on the contrary, the aqueous phase may be added dropwise to the oil phase by the phase inversion emulsification method. This is also preferable in the present invention. When the dye used in the present invention is water-soluble and the additive is oil-soluble, an emulsification method may be used.

Various surfactants may be used in the emulsification. For example, a fatty acid salt, an alkyl sulfate salt, an alkylbenzene sulfonate salt, an alkyl naphthalene sulfonate salt, a dialkyl sulfosuccinate salt, an alkyl phosphate salt, a naphthalene sulfonate-formalin condensate, a polyoxyethylene alkyl sulfate salt, etc. Anionic surfactants; And polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, glycerin fatty acid esters, oxyethylene-oxypropylene block air Nonionic surfactants, such as coalescence, are preferable. Also preferred are acetylene-based polyoxyethylene oxide surfactants and Surfynols (manufactured by Air Products & Chemicals). Moreover, amine oxide type amphoteric surfactants, such as N, N- dimethyl-N-alkylamine oxide, are also preferable. Furthermore, Japanese Patent Laid-Open No. 59-157636, pp. 37-38; And surfactants described in Research Disclosure No. 308119 (1989) can also be used.

In order to stabilize the emulsion just after the preparation, a water-soluble polymer may be added together with the above-mentioned surfactant. Preferred examples of the water-soluble polymers include polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, polyacrylic acid, polyacrylamide and copolymers thereof. In addition, natural water-soluble polymers such as polysaccharides, casein and gelatin are also preferably used. In order to stabilize dye dispersion, polymers substantially insoluble in an aqueous medium such as polyvinyl compounds, polyurethanes, polyesters, polyamides, polyureas, polycarbonates, and acrylates, Those obtained by polymerizing methacrylates, vinyl ethers, acrylamides, methacrylamides, olefins, styrenes, vinyl esters, acrylonitriles and the like can be further used. Preferably, these polymers are -SO ₃ ^- has a ^- or -COO. When using such a polymer that is not substantially dissolved in an aqueous medium, the amount of use is preferably at most 20% by weight, more preferably at most 10% by weight relative to the weight of the high boiling organic solvent.

In the case of producing an aqueous ink by emulsifying and dispersing an oil-soluble dye and a high boiling point organic solvent, it is very important to control the particle size of the dye dispersion. In order to increase the color purity and density of the image formed by the inkjet, it is essential to reduce the average particle size of the dye particles in the inkjet ink. Preferably, the volume average particle size of the dye particles is at most 1 μm, more preferably 5 to 100 nm.

The volume average particle size and particle size dispersion degree of the dispersed dye particles can be easily obtained by a known method. For example, the method described in Lecture of Experimental Chemistry , 4th edition, pp. 417-418 can be used, as well as the static light scattering method, the dynamic light scattering method, the centrifugal precipitation method. Specifically, the ink samples are diluted with distilled water so that the dye particle concentration is 0.1 to 1% by weight, and then the particle size of the pigment particles is determined by using a commercially available optimum average particle size measuring device (eg, Microtrack UPA, manufactured by Nikkiso). . In the above measurement, the dynamic light scattering method based on the laser Doppler effect is particularly preferable because it can measure even small particles.

The volume average particle size is the average particle size measured by the volume of the particles. This is the total sum of the values obtained by multiplying the diameter of each aggregated particle by its volume and dividing the total of the whole particles. Volume average particle sizes are described, for example, in S. Muroi, Chemistry of Polymer Latex , published by Polymer, p. 119.

It has been found that coarse particles have a significant effect on the printability of the ink. Specifically, by coarse particles clogging the head or contaminating the head even if it is not blocked, ink cannot be ejected at all or is unevenly ejected. With this effect, the coarse particles have a significant effect on the printability of the ink. In order to avoid this problem, it is important to contain up to 10 particles having a particle size of 5 μm or more and up to 1000 particles having a particle size of 1 μm or more in 1 μl of ink.

In order to remove such coarse particles, for example, known centrifugation or microfiltration can be used. The coarse particle removal treatment may be performed immediately after the emulsion dispersion of the ink, or after adding various additives such as a humidifier and a surfactant to the emulsion dispersion, and immediately before filling the ink cartridge with the obtained ink. good.

In order to effectively reduce the average particle diameter and to remove coarse particles, a mechanical emulsifying device can be used.

Examples of the emulsifying apparatus include mills such as known ones, such as simple stirrers, impeller assisted stirrers, inline stirrers, colloid mills, and ultrasonic stirrers. Of these, high pressure homogenizers are particularly preferred.

The mechanism of the high pressure homogenizer is described in detail in, for example, US Patent No. 4,533,254 and Japanese Patent Laid-Open No. 6-47264. Gaulin Homogenizer (manufactured by A.P.V.Gaulin), Microfluidizer (manufactured by Microfluidex) and Ultramizer (manufactured by Sugino Machine) are commercially available.

In recent years, U.S. Patent No. 5,720,551 discusses high-pressure homogenizers equipped with a mechanism for atomizing fine particles in ultra-high pressure jets, and these are preferable for the emulsion dispersion treatment in the present invention. An emulsifying apparatus equipped with such an ultra-high pressure jet flow mechanism is DeBEE2000 (Bee International).

The pressure at the time of emulsification in such a high pressure emulsion dispersion apparatus is 50 MPa or more, preferably 60 MPa or more, more preferably 180 MPa or more.

In this invention, it is especially preferable to use 2 or more types of emulsifying apparatuses. For example, the components are first emulsified in a stirred emulsifier and then further emulsified in a high pressure homogenizer. In addition, once the components are emulsified in the emulsifying apparatus as described above, an additive such as a moisturizer or a surfactant is added to the obtained emulsion, and then further emulsified in a high pressure homogenizer before filling the cartridge with the obtained ink. The method of doing is also preferable.

When using the low boiling point organic solvent together with the high boiling point organic solvent as mentioned above, it is preferable to remove the low boiling point solvent from the emulsion in order to ensure the safety, stability, and hygiene of the emulsion. In removing a low boiling point solvent, various methods can be used according to the kind of solvent to be removed. For example, evaporation, vacuum evaporation or ultrafiltration can be used. The low boiling organic solvent is preferably removed as soon as possible immediately after preparation of the emulsion.

About the manufacturing method of an inkjet ink, it is described in detail in Unexamined-Japanese-Patent No. 5-148436, 5-5-535312, 7-97541, 7-82515, and 7-118584, for example. The description is applicable to the production of the ink of the present invention.

The ink of the present invention may contain various functional components that impart various functions to the ink. For example, the functional component may include not only the various solvents described above, but also a drying inhibitor for inhibiting the ink from drying in the inkjet nozzle orifices and clogging the nozzle, a penetration accelerator for promoting the permeability of the ink into paper, and a UV absorber and an antioxidant. Thickeners, surface tension enhancers, dispersants, dispersion stabilizers, antifungal agents, rust inhibitors, pH adjusters, antifoaming agents, chelating agents. The ink of the present invention may contain an appropriately selected one of them. Some functional components may exhibit one or more functions alone. Therefore, in the compounding ratio of the functional component in the ink of this invention mentioned later, the functional component which has a multiple function alone calculates each function independently.

As a drying inhibitor, the water-soluble organic solvent which has a vapor pressure lower than water is preferable. Specific examples thereof include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, Polyhydric alcohols such as acetylene glycol derivatives, glycerin, and trimethylolpropane; Polyhydric alcohol lower alkyl ethers such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether and triethylene glycol monoethyl (or butyl) ether; Heterocyclic compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and N-ethylmorpholine; Sulfur-containing compounds such as sulfolane, dimethyl sulfoxide and 3-sulforene; Polyfunctional compounds such as diacetone alcohol and diethanolamine; And urea derivatives. Among these, polyhydric alcohols, such as glycerin and diethylene glycol, are more preferable. One or more of these drying inhibitors may be used alone or in combination. Content of the drying agent of an ink becomes like this. Preferably it is 10-50 weight%.

Examples of penetration accelerators that can be used herein include alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether and 1,2-hexanediol; And nonionic surfactants such as sodium lauryl sulfate and sodium oleate. Usually, the amount of penetration accelerator in the ink is 10 to 30% by weight is sufficient. However, the amount is preferably adjusted to such an extent that the ink does not cause bleeding and shimmering.

Ultraviolet absorbers are for improving image stability. As a ultraviolet absorber, the benzotriazole compound of Unexamined-Japanese-Patent No. 58-185677, 61-190537, 2-782, 5-197075, 9-34057; Benzophenone compounds described in Japanese Patent Application Laid-Open Nos. 46-2784, 5-194483, and US Patent No. 3214463; Cinnamate compounds described in JP-A-48-30492, 56-21141, and JP-A-10-88106; The triazine compounds described in JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A 10-182621, and PCT JP-A-8-501291; The compounds described in Research Disclosure 24242; And a compound capable of absorbing ultraviolet rays represented by stilbene compounds and benzoxazole compounds to emit fluorescence, that is, fluorescent brighteners.

Antioxidants are intended to improve burn stability. Various organic or metal complex type | mold fading inhibitor can be used as it. Examples of the organic fading inhibitors include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, phosphorus groups, cromanns, alkoxyanilines and heterocyclic compounds; Metal complexes include nickel complexes and zinc complexes. More specifically, in Research Disclosures No.17643, VII-I to J, No. 15162, No. 18716, p.650 left column, No. 36544, p.527, 307105, p.872 and 15162 In addition to the compounds described in the cited patent publications, the compounds within the ranges of the general formulas representing the typical compounds described in pp. 127 to 137 of JP-A-62-215272 and examples of the compounds can be used.

Antifungal agents include sodium dihydroacetate, sodium benzoate, sodium pyridinthione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof. The amount in the ink is preferably 0.02 to 5.00% by weight.

The details are described, for example, in Dictionary of Antibacterials and Antifungals (published by Dictionary Section of the Antibacterial and Antifungal Society of Japan).

Examples of the rust inhibitors include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and benzotriazole. The amount in the ink is preferably 0.02 to 5.00% by weight.

pH adjusters are preferably used for pH adjustment and dispersion stabilization. The pH of the ink is preferably adjusted within the range of 8 to 11 at 25 ° C. If the pH is less than 8, the dye solubility is lowered and the nozzle is clogged quickly. However, when the pH exceeds 11, the water resistance of the ink is deteriorated. The pH adjuster may be a basic compound such as an organic base and an inorganic alkali, or an acidic compound such as an organic acid and an inorganic acid.

Basic compounds include, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, sodium phosphate, sodium hydrogen phosphate and other inorganic compounds, Ammonia water, methylamine, ethylamine, diethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, ethylenediamine, piperidine, diazabicyclooctane, diazabicycloundecene, pyridine, quinoline, picoline , Rutidine, collidine and other organic bases.

Examples of the acidic compound include inorganic compounds such as hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, sodium hydrogen sulfate, potassium hydrogen sulfate, potassium dihydrogen phosphate and sodium dihydrogen phosphate; And organic compounds such as acetic acid, tartaric acid, benzoic acid, trifluoroacetic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, saccharic acid, phthalic acid, picolinic acid and quinoline acid.

The conductivity of the ink of the present invention is within 0.01 to 10 S / m, preferably within 0.05 to 5 S / m.

Conductivity can be measured by the electrode method using commercially available saturated potassium chloride.

The conductivity is adjustable according to the ion concentration of the aqueous solution. If the salt concentration is high, the solution may be desalted by ultrafiltration. When adding a salt etc. in order to adjust the conductivity of a solution, you may use various organic salts or inorganic salts according to the objective.

Inorganic or organic salts include, for example, potassium halides, sodium halides, sodium sulfates, potassium sulfates, sodium hydrogensulfate, potassium hydrogensulfate, sodium nitrate, potassium nitrate, potassium bicarbonate, sodium phosphate, sodium monohydrogen Inorganic compounds such as phosphate, borate, potassium dihydrogen phosphate and sodium dihydrogen phosphate; And organic compounds such as sodium acetate, potassium acetate, potassium tartrate, sodium tartrate, sodium benzoate, potassium benzoate, sodium p-toluenesulfonate, potassium saccharate, potassium phthalate, sodium picolinate and the like.

Moreover, you may specifically select and adjust the component of the aqueous medium which mentions the conductivity of ink later.

The viscosity of the ink of this invention is 25-30 degreeC, Preferably it is 1-30 mPa * s, More preferably, it is 2-15 mPa * s, More preferably, it is 2-10 mPa * s. When the viscosity exceeds 30 mPa · s, the fixing of the recording image may be delayed, and the ink discharging performance is also lowered. If the viscosity is less than 1 mPa · s, blur occurs on the recording image, and the quality thereof is deteriorated.

The viscosity can be adjusted to a desired degree by adjusting the amount of the ink solvent. Examples of the ink solvent include glycerin, diethylene glycol, triethanolamine, 2-pyrrolidone, diethylene glycol monobutyl ether, and triethylene glycol monobutyl ether.

As needed, you may use a thickener. Examples of the thickener include water-soluble polymers such as cellulose and polyvinyl alcohol and nonionic surfactants. Details thereof are described, for example, in Viscosity Control Technology (Technology Information Association, 1999), Chapter 9; Chemicals for Inkjet Printers (1998 Supplement) —Investigation of Trends and Views in Development of Materials (published by CMC, 1997), pp. 162-174.

The method for measuring the viscosity of a liquid is described in detail in JIS Z8803. In the present invention, the viscosity of the ink can be easily measured in a simple manner using a commercially available viscometer. For example, there are a type B viscometer and a type E viscometer which are rotary viscometers manufactured by known Tokyo Instrument. In this invention, the viscosity was measured at 25 degreeC using the VM-100A-L type | mold which is a vibratory viscometer by Yamaichi Electric. The unit of viscosity is pascal seconds (Pa · s), but usually, millipascal seconds (mPa · s).

The surface tension of the ink of the present invention is preferably 20 to 50 mN / m at 25 ° C. for both dynamic and static surface tension. More preferably, it is 20-40 mN / m. When the surface tension exceeds 50 mN / m, the ejection stability of the ink is deteriorated. In addition, printing formed by mixing multiple colors becomes blurry and smeared, resulting in a markedly lower print quality. On the other hand, if the surface tension is less than 20 mN / m, ink adheres to the surface of the printer tool, resulting in poor print quality.

In order to adjust the surface tension of the ink, various cationic, anionic, nonionic or betaine-based surfactants as described above may be added to the ink. If necessary, two or more different kinds of surfactants may be used in combination in the ink.

As a method of measuring the static surface tension of an ink, the capillary raising method, the dropping method, and the redundancy method are known. In the present invention, the static surface tension of the ink is measured according to the vertical plate method.

In brief, when a thin plate of glass or platinum is immersed in a portion of the liquid and vertically hung, the surface tension of the liquid acts downward along the portion where the liquid and the plate come into contact. The surface tension of the liquid is obtained by balancing the force of the surface tension with the force acting upward.

The dynamic surface tension of the ink is measured, for example, by vibrating jet method and menis as described in Lecture of New Experimental Chemistry , Vol. 18, "Interface and Colloid" (Maruzen), pp. 69-90 (1977). The miniscus drop method and the maximum bubble pressure method are known. In addition, a liquid film destruction method such as described in, for example, Japanese Patent Laid-Open No. 3-2064 is known. In the present invention, the dynamic surface tension of the ink is measured according to the bubble pressure difference method. The principle and mechanism of this method are described below.

When bubbles are generated in a uniform solution prepared by stirring, a new gas-liquid interface is formed, and the surfactant molecules in the solution gather at a constant rate around the surface of water. Under this condition, the bubble speed (bubble generation rate) is changed. When the bubble speed is slowed down, more surfactant molecules are gathered on the surface of the formed bubble, and the maximum bubble pressure just before the bubble bursts becomes small. The maximum bubble pressure (surface tension) is detected with respect to the bubble velocity. An example of measuring the dynamic surface tension of an ink is as follows: A large probe and a small probe are used to form a bubble in the ink using a total of two probes. The differential pressure in the state of the maximum bubble pressure of two probes is measured, and dynamic surface tension is computed from this.

The nonvolatile component of the ink of the present invention is preferably 10 to 70% by weight of the ink in order to secure the ejection stability and good print quality of the ink in terms of image fastness, image blur resistance and non-stickiness of the printed matter. More preferably, 20 to 60% by weight is more preferable in order to ensure the ejection stability of the ink and to secure the excellent print quality in terms of the image blur resistance of the printed matter.

Non-volatile components include liquid and solid components having a boiling point of 150 ° C. or higher at 1 atm, and polymer components. Non-volatile components of inkjet recording inks include dyes, high boiling point solvents and other polymer latexes, surfactants, dye stabilizers, antifungal agents and buffers added as needed. Most of these nonvolatile components, except dye stabilizers, lower the dispersion stability of the ink and remain on printing paper, inhibiting the association and stabilization of the dye, resulting in deterioration of image fastness, and images printed under high humidity conditions. The blur often occurs.

The ink of the present invention may contain a polymer compound. The polymer compound refers to any and all polymer compounds having a number average molecular weight of 5000 or more in the ink. Polymer compounds include water-soluble polymer compounds substantially dissolved in an aqueous medium, water-dispersible polymer compounds such as polymer latex and polymer emulsions, as well as alcohol-soluble polymer compounds dissolved in a polyhydric alcohol used as an auxiliary solvent. Any polymer compound may be present in the ink in the present invention as long as it is substantially dissolved or dispersed uniformly in the ink.

Examples of the water-soluble polymer compound include polyalkylene oxides such as polyvinyl alcohol, silanol-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinylpyrrolidone, polyethylene oxide and polypropylene oxide, and polyalkylene oxides. Derivatives and other water-soluble polymers; Natural water-soluble polymers such as polysaccharides, starch, cationic starch, casein, gelatin; Aqueous acrylic resins such as polyacrylic acid, polyacrylamide and copolymers thereof; There are aqueous alkyd resins and other water soluble polymer compounds having -SO ₃ ^- or -COO ^- in the molecule and substantially dissolved in the aqueous medium.

Examples of the polymer latex include styrene-butadiene latex, styrene-acrylic latex and polyurethane latex. Polymer emulsions include acrylic emulsions and the like.

These water soluble polymer compounds may be used alone or in combination.

As described above, the water-soluble polymer compound is used as a thickener for controlling the viscosity of the ink into a suitable viscosity region in order to secure good discharge characteristics of the ink. However, if the ink contains too much of the compound, the ink viscosity increases and the ejection stability of the ink deteriorates. In addition, ink may form a deposit at the time of storage, and a nozzle may be clogged.

The amount of the polymer compound added to the ink for viscosity adjustment depends on the molecular weight of the compound (the higher the molecular weight, the smaller the amount), but is 0 to 5% by weight of the ink. Preferably it is 0-3 weight%, More preferably, it is 0-1 weight%.

In the present invention, various cationic, anionic, nonionic and betaine-based surfactants as described above may be used as dispersants and dispersion stabilizers, and chelating agents such as fluorine-containing compounds, silicone compounds and EDTA, if necessary. May be used as an antifoaming agent.

As the printing medium used in the present invention, a reflective medium is preferable. Examples of the reflection medium include recording paper and recording film. The support of the recording paper and the recording film includes chemical pulp such as LBKP and NBKP; Mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMP, CGP; Or recycled paper pulp such as DIF. As needed, you may add well-known additives, such as a pigment, a binder, a sizing agent, a fixing agent, a cationic agent, and an intelligence enhancer. Various paper machines, such as a Fourdrinier paper machine and a cylindrical paper machine, can be used for preparing the support. In addition to these supports, synthetic paper and plastic film sheets may also be used. Preferably the thickness of a support body is 10-250 micrometers, and a unit weight is 10-250 g / m <^2> .

The water phase layer and the black coating layer may be directly formed on the support to produce the water and ink set material for ink set of the present invention. If necessary, after the size press or anchor coating is applied to the support with starch, polyvinyl alcohol, or the like, the water support layer and the black coating layer are coated on the support to obtain an aqueous material used in the present invention. If necessary, the support may be planarized by mechanical calendaring, TG calendaring, soft calendaring, or the like.

As a support body used for this invention, the paper and plastic film in which both sides laminated | stacked polyolefin (for example, polyethylene, polystyrene, polybutene or its copolymer) or polyethylene terephthalate are more preferable. Also preferably, a white dye (eg titanium oxide, zinc oxide) or a coloring dye (eg cobalt blue, ultramarine, neodium oxide) is added to the polyolefin.

The aqueous layer formed on the support contains a porous material and an aqueous binder. Preferably the aqueous layer contains a pigment. As a pigment, a white pigment is preferable. White pigments include potassium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, barium sulfate, calcium sulfate, titanium dioxide, zinc Inorganic white pigments such as sulfide and lead carbonate; And organic white pigments such as styrene pigments, acrylic pigments, urea resins and melamine resins. Particular preference is given to porous inorganic white pigments, most preferably synthetic amorphous silica with large pores. Synthetic amorphous silica may be either anhydrous silica obtained by a dry production method (gas phase method) or a hydrous silica obtained by a wet production method.

Examples of the recording paper containing the pigment described above in the aqueous layer include, for example, Japanese Patent Application Laid-Open Nos. 10-81064, 10-119423, 10-157277, 10-217601, 11-348409, 2001-138621, 2000-43401, 2000-211235, 2000-309157, 2001-96897, 2001-138627, Flat 11-91242, Flat 8-2087, Flat 8-2090, Flat 8 -2091, 8-2093, 8-174992, 11-192777, 2001-301314, and any of these may be used.

The aqueous binder contained in the aqueous phase includes polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, polyvinylpyrrolidone, polyalkylene oxide Water-soluble polymers such as polyalkylene oxide derivatives; And water dispersible polymers such as styrene-butadiene latex and acrylic emulsion. You may use 1 or more types of these aqueous binders individually or in combination. Among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to pigments and peeling resistance of the ink receiving layer.

In addition to the pigment and the aqueous binder, the aqueous layer may contain any other additives such as a mordant, a water repellent, a light fastness enhancer, a gas resistance improver, a surfactant, a film film and the like.

It is preferable that the mordant in an aqueous layer is passivated. Specifically, polymer mordant is preferred.

As for the polymer mordant, for example, Japanese Patent Application Laid-Open Nos. 48-28325, 54-74430, 54-124726, 55-22766, 55-142339, 60-23850, and 60-23851 , SO 60-23852, SO 60-23853, SO 60-57836, SO 60-60643, SO 60-118834, SO 60-122940, SO 60-122941, SO 60-122942, SO 60-235134, Japanese Patent Application Laid-Open No. 1-61236; US Patent Nos. 2,484,430, 2,548,564, 3,148,061, 3,309,690, 4,115,124, 4,124,386, 4,193,800, 4,273,853, 4,282,305, 4,450,224. The polymer mordant described in pp. 212 to 215 of Japanese Patent Application Laid-Open No. Hei 1 -61236 is particularly preferable for the water receiving material of the present invention. This gives a good quality image and light fastness.

Water repellents are effective for imparting resistance to water in burns. As the water resistant agent, cationic resins are particularly preferred. Examples of this cationic resin include polyamide-polyamine-epichlorohydrin, polyethylene-imine, polyamine-sulfone, dimethyldiallylammonium chloride polymer and cationic polyacrylamide. 1-15 weight% is preferable with respect to the total solid of an ink receiving layer, and, as for content of cationic resin of an ink receiving layer, 3-10 weight% is more preferable.

As light fastness improvers and gas resistance improvers, for example, a phenol compound, a hindered phenol compound, a thioether compound, a thiourea compound, a thiocyanate compound, an amine compound, a hindered amine compound, a TEMPO compound, a hydrazine compound, a hydrazide compound , Amidine compounds, vinyl-containing compounds, ester compounds, amide compounds, ether compounds, alcohol compounds, sulfinate compounds, sugars, water-soluble reducing compounds, organic acids, inorganic acids, hydroxy-containing organic acids, benzotriazole compounds, benzophenone compounds, Triazine compounds, heterocyclic compounds, water-soluble metal salts, organometallic compounds, and metal complexes.

As a specific example of these compounds, Unexamined-Japanese-Patent No. 10-182621, 2001-260519, 2000-260519; Japanese Patent Publication Nos. Hei 4-34953, Hei 4-34513, Hei 4-34512; Japanese Patent Laid-Open Nos. 11-170686, 60-67190, 7-276808, 2000-94829; PCT Patent Application Publication No. Hei 8-512258; It is described in Unexamined-Japanese-Patent No. 11-321090.

The surfactant functions as a coating aid, a peelability improving agent, a smoothness improving agent or an antistatic agent. For example, Japanese Patent Laid-Open Nos. 62-173463 and 62-183457 are described.

Instead of the surfactant, an organic fluorine-containing compound may be used. The organofluorine-containing compound used here is preferably hydrophobic. Examples of organofluorine-containing compounds include fluorine-containing surfactants, oily fluorine-containing compounds (eg fluorine oils) and solid fluorine-containing compound resins (eg tetrafluoroethylene resins). For organic fluorine-containing compounds, Japanese Patent Publication No. 57-9053 (Columns 8 to 17); Japanese Patent Application Laid-Open Nos. 61-20994 and 62-135826.

As the film-forming agent, those described in p. 222 of Japanese Patent Application Laid-Open No. Hei 1-61236, Hei 9-263036, Hei 10-119423 and 2001-310547 can be used.

Other additives in the aqueous phase include pigment dispersants, tackifiers, defoamers, dyes, optical brighteners, preservatives, pH adjusters, matting agents and dura mater. The ink receiving material may have one or more ink receiving layers.

The recording paper and the recording film may have a back coat layer. This layer may contain a white pigment, an aqueous binder, and other components.

Examples of the white pigment in the backcoat layer include hard calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate Inorganic white pigments such as magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudo-boehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrated halosite, magnesium carbonate and magnesium hydroxide; And organic white pigments such as styrene plastic pigments, acrylic plastic pigments, polyethylene microcapsules, urea resins, melamine resins, and the like.

As the aqueous binder in the backcoat layer, for example, styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationic starch, casein, gelatin, carboxymethyl cellulose, hydroxide Water-soluble polymers such as oxyethyl cellulose and polyvinylpyrrolidone; And water dispersible polymers such as styrene-butadiene latex and acrylic emulsion. Other components in the back coat layer include antifoaming agents, defoamers, dyes, optical brighteners, preservatives, water resistant agents and the like.

A dispersion of polymer particles may be added to the constituent layers (including the white layer) of the inkjet recording paper and the film of the present invention. The polymer particle dispersion is, for example, to improve the dimensional stability of the layer, and to improve the physical properties of the coating layer such as preventing the layer from curling, blocking and cracking. The polymer particle dispersion is described in Japanese Patent Laid-Open Nos. 62-245258, 62-1316648, and 62-110066. Adding a polymer particle dispersion having a low glass potential temperature (below 40 ° C.) to a mordant containing layer is effective in preventing the layer from cracking and curling. In addition, even when a polymer particle dispersion having a high glass potential temperature is added to the back layer, it is effective to prevent the layer from curling.

The present invention can be used for other purposes than for inkjet recording. For example, it can be used for display image forming, indoor decoration image forming, and outdoor decoration image forming.

For display image forming purposes, posters, wallpaper, decorative props (e.g. decorations, figurines), advertising flyers, wrapping paper, packaging materials, paper bags, plastic bags, packing materials, signs, transportation agencies (cars, buses, As well as an image formed on a cloth or the like containing a logo. When the dye of the present invention is used to form such a display image, the image includes not only the narrow meaning of the word but also all the color patterns that an abstract design, letters, geometric patterns, etc. can be recognized by human beings.

As an image forming upholstery material, it means a variety of articles such as wallpaper, decorative props (eg, ornaments, dolls), lighting fixtures, furniture parts, design parts for floors and ceilings. When the dye of the present invention is used to form an image on such a material, the image includes not only the narrow meaning of the word, but also any color pattern that an abstract design, letters, geometric patterns, and the like can be perceived by humans. do.

As an outdoor decorative material for image forming, it means various articles such as a wall material, a roof material, a signboard, a landscaping material, an outdoor decorative accessory (for example, a decoration, a doll), and a part of an outdoor lighting device. When the dye of the present invention is used to form an image on such a material, the image includes not only the narrow meaning of the word, but also all the color patterns that an abstract design, letters, geometric patterns, and the like can be perceived by humans. .

In the above uses, the patterned media include paper, fibers, fabrics (including nonwoven fabrics), plastics, metals, ceramics and other various materials. In the dyeing form, the dye can be applied and immobilized in any form of mordant, printing or chemical reaction of the reactive dye with the reactive groups introduced therein. Among these, the mordant form which fixes a dye on a medium is especially preferable.

In the production of the ink of the present invention, ultrasonic waves can be applied to a system in which dyes and additives are dissolved in a medium.

Ultrasonic vibrations during ink production are for removing bubbles from the ink. This is because bubbles are sometimes generated when ink is pressurized from the recording head. To prevent this, bubbles are removed by applying to the ink ultrasonic waves equal to or more than the energy received from the recording head in advance.

The frequency of the ultrasonic vibration is usually 20 kHz or more, preferably 40 kHz or more, and more preferably 50 kHz or more. The energy applied to the ink by the ultrasonic vibration is usually 2 × 10 ⁷ J / m ³ or more, preferably 5 × 10 ⁷ J / m ³ or more, and more preferably 1 × 10 ⁸ J / m ³ or more. The ultrasonic vibration time is usually about 10 minutes to 1 hour.

The effect of ultrasonic vibrations can occur at any time after the dye has been added to the medium. After preserving the finished ink, it is effective even if exposed to ultrasonic waves. However, applying ultrasonic waves while dissolving and / or dispersing the dye in the medium is more preferable because the effect of defoaming is greater and promotes dissolution and / or dispersion of the dye in the medium.

Therefore, the sonication can be performed in any step during or after the step of dissolving and / or dispersing the dye in the medium. That is, the ultrasonic treatment can be performed one or more times at any time between the preparation of the ink and the completion of the commercial product.

In a preferred embodiment of the present invention, the process of dissolving and / or dispersing the dye in the medium comprises dissolving the dye in a portion of the medium and mixing the remaining medium with the resulting dye solution. It is preferred to apply ultrasound to the system in one or more of these steps. More preferably, ultrasonication is applied to the system in the former step of dissolving the dye in a portion of the medium.

The latter step of mixing the residual medium and the obtained dye solution may be a single step or a plurality of steps.

In the production of the ink of the present invention, it is preferable to degas the system under heating or under reduced pressure. This is preferable because the air bubbles are more effectively removed from the ink. The step of degassing the system under heating or under reduced pressure is preferably carried out simultaneously with or after the step of mixing the previously prepared dye solution and the residual medium.

The ultrasonic waves applied to the ink manufacturing system may be generated using a known ultrasonic wave machine.

In the production of the ink of the present invention, it is also important to filter the produced ink composition to remove impurities. In this process, a filter is used. The effective pore size of the filter is at most 1 μm, preferably 0.05 to 0.3 μm, more preferably 0.25 to 0.3 μm. Various materials can be used for forming a filter. Especially for the ink of water-soluble dye, the filter specially manufactured for the aqueous solvent is preferable. More preferably, the filter is made of a polymer material capable of trapping impurities well. In filtration, the ink composition may be passed through a filter in a usual liquid feeding form. In addition, you may use other forms of pressure filtration or pressure filtration.

After filtration, air is often injected into the ink. Bubbles caused by this air often degrade the image during inkjet recording. Therefore, it is preferable to further perform a process for further degassing the ink as described above. As the degassing method, for example, it may be allowed to stand for a while after filtration, or may be degassed ultrasonically or under reduced pressure using a commercially available apparatus. It is preferable to perform 30 seconds-2 hours of ultrasonic degassing, More preferably, it is about 5 minutes-about 1 hour.

These treatments are preferably performed in a clean room or in a clean bench space in order to prevent the ink from being contaminated with impurities during the treatment. In the present invention, the above treatment is preferably performed in a space having a maximum cleanliness of class 1000. "Cleanness" refers to the value measured by the dust counter.

The dot volume of the ink on the recording material in the present invention is 0.1 to 100 pl, more preferably 0.5 to 50 pl, still more preferably 2 to 50 pl.

The method of the inkjet recording method using the ink or ink set of the present invention using an inkjet printer is not particularly limited, and a known method can be used. For example, the charge control method for discharging the ink through the electrostatic attraction; A drop-on-demand method (pressure pulse method) using vibration pressure of a piezoelectric element; An acoustic inkjet method for converting an electric signal into an acoustic beam, applying this to ink, and ejecting ink under radial pressure; Both thermal inkjets (bubble inkjets) that heat the ink to form bubbles and utilize the resulting pressure can be used.

The inkjet recording methods include a method of ejecting a large amount of small droplets of a low density photo ink, a method of improving image quality using a plurality of inks substantially different in the same color or density, and a method of using colorless transparent ink. . The dot volume on the recording material is mainly controlled by the print head.

For example, in the thermal inkjet method, the dot volume can be controlled according to the structure of the print head. Specifically, the dot volume can be changed into a predetermined shape by changing the ink chamber, the heating part and the nozzle size. When a plurality of print heads having different heating parts and nozzle sizes are used in the thermal inkjet method, ink droplets having different sizes can be realized.

In a drop-on-demand system using a piezoelectric element, the dot volume may vary depending on the structure of the printhead as in the thermal inkjet method as described above. However, in this, the waveform of the drive signal of the piezoelectric element is controlled as described later, so that ink droplets of different sizes can be realized through the print head of the same structure.

When the ink of the present invention is discharged dropwise onto the recording material, the discharge frequency is preferably 1 kHz or more.

In order to obtain high-quality pictures, small ink drops are used to reproduce sharp and high-quality pictures. To do this, the dot density must be at least 600 dpi (dots per inch).

On the other hand, in the recording system in which ink is discharged through the heads having a plurality of row lines, and the recording paper is moved vertically with respect to the head, the number of heads that can be driven simultaneously is about 10 to 200. Even in a line head system in which a plurality of heads are fixed, the number of heads that can be driven simultaneously is limited to hundreds. Since the driving force is not limited, a plurality of head nozzles cannot be driven at the same time because some may affect the image in which the heat of the head is formed.

As the driving frequency increases, the recording speed may increase.

In order to adjust the inkjet frequency in the thermal inkjet system, the frequency of the head drive signal is controlled to heat the head.

In the piezoelectric method, the frequency of a signal is controlled to drive the piezoelectric element.

The driving mechanism of the piezoelectric head will be described. The image signal for printing is controlled by the printer control unit in terms of dot size, dot speed and dot frequency, so that a signal for driving the print head is formed. The drive signal thus formed is directed to the print head. The piezoelectric drive signal controls the dot size, dot speed and dot frequency. The dot size and the dot speed are determined by the shape and amplitude of the driving waveform, and the frequency is determined by the repetition period of the signal.

When the dot frequency is set to 10 kHz, the head is driven in every 100 microseconds, and one line recording is completed at 400 microseconds. If the moving speed of the recording paper is set to move 1/600 inches, that is, about 42 microns per 400 microseconds, one sheet can be printed every 1.2 seconds.

In the configuration of the printing apparatus and the configuration of the printer used in the present invention, for example, embodiments in Japanese Patent Laid-Open No. 11-170527 are preferably listed. As ink cartridges, for example, those disclosed in Japanese Patent Laid-Open No. 5-229133 are preferable. As for the configuration of the suction mechanism during printing and the configuration of the cap covering the printing head, those described in, for example, Japanese Patent Application Laid-open No. Hei 7-276671 are preferably listed. In addition, it is preferable that a bubble removing filter is provided in the vicinity of the head as in Japanese Patent Laid-Open No. 9-277552.

The nozzle surface is preferably subjected to a water repellent treatment as in Japanese Patent Laid-Open No. 2001-292878. In this use, the ink of the present invention can be used in a printer connected to a computer, or in a printer specially designed for photography only.

In the inkjet recording method of the present invention, it is preferable that ink is discharged to the recording material at an average dot speed of 2 m / sec or more, more preferably 5 m / sec.

In order to control the dot speed, the shape and amplitude of the head driving waveform can be controlled.

When a plurality of drive waveforms having different shapes are selectively used in one printer, ink dots having different sizes can be discharged through the same head of the printer.

Although this invention is demonstrated with reference to the following Example, this invention is not limited to this.

(Example 1)

Ultrapure water (resistance, 18 MΩ or more) was added to the component described later so as to be 1 L, followed by stirring for 1 hour while heating to 30 to 40 ° C. The resulting mixture was then filtered under reduced pressure through a micro filter having an average pore size of 0.25 μm. Ink of each color was thus prepared.

[Prescription of Light Cyan Ink, LC-101]

(Solid components)

Cyan dye (C-1) 20 g / L

Urea (UR) 15g / L

Benzotriazole (BTZ) 0.08 g / L

Proxel XL2 (PXL) 3.5g / L

(Liquid component)

Triethylene glycol (TEG) 110 g / L

Glycerin (GR) 130 g / L

Triethylene glycol monobutyl ether (TGB) 110 g / L

2-pyrrolidone (PRD) 60 g / L

Triethanolamine (TEA) 7 g / L

Surfinol STG (SW) 10g / L

[Prescription of Cyan Ink, C-101]

(Solid components)

Cyan Dye (C-1) 60g / L

Urea (UR) 30 g / L

Benzotriazole (BTZ) 0.08 g / L

Proxel XL2 (PXL) 3.5g / L

(Liquid component)

Triethylene glycol (TEG) 110 g / L

Glycerin (GR) 130 g / L

Triethylene glycol monobutyl ether (TGB) 130 g / L

2-pyrrolidone (PRD) 60 g / L

Triethanolamine (TEA) 7 g / L

Surfinol STG (SW) 10g / L

[Prescription of Light Magenta Ink LM-101]

(Solid components)

Magenta Dye (M-1) 7.5g / L

Urea (UR) 10g / L

Proxel 5g / L

(Liquid component)

Diethylene glycol (DEG) 90 g / L

Glycerin (GR) 70 g / L

Triethylene glycol monobutyl ether (TGB) 70 g / L

Triethanolamine (TEA) 6.9 g / L

Surfinol STG (SW) 10g / L

[Prescription of Magenta Ink, M-101]

(Solid components)

Magenta Dye (M-1) 23g / L

Urea (UR) 15g / L

Proxel 5g / L

(Liquid component)

Diethylene glycol (DEG) 90 g / L

Glycerin (GR) 70 g / L

Triethylene glycol monobutyl ether (TGB) 70 g / L

Triethanolamine (TEA) 6.9 g / L

Surfinol STG (SW) 10g / L

[Yellow Ink, Y-101 Prescription]

(Solid components)

Yellow dye (Y-1) 35 g / L

Proxel 3.5g / L

Benzotriazole (BTZ) 0.08 g / L

Urea 10g / L

(Liquid component)

Triethylene glycol monobutyl ether (TEG) 130 g / L

Glycerin (GR) 115 g / L

Diethylene glycol (DEG) 120 g / L

2-pyrrolidone 35g / L

Triethanolamine (TEA) 8 g / L

Surfinol STG (SW) 10g / L

[Dark yellow ink, prescription of DY-101]

(Solid components)

Yellow dye (Y-1) 35 g / L

Magenta dye (M-1) 2 g / L

Cyan dye (C-1) 2 g / L

Proxel 5g / L

Benzotriazole (BTZ) 0.08 g / L

Urea 10g / L

(Liquid component)

Triethylene glycol monobutyl ether (TGB) 140 g / L

Glycerin (GR) 125 g / L

Diethylene glycol (DEG) 120 g / L

2-pyrrolidone (PRD) 35 g / L

Triethanolamine (TEA) 8 g / L

Surfinol STG (SW) 10g / L

[Prescription of Black Ink, Bk-101]

(Solid components)

75 g / L of black dye (Bk-1)

Black dye (Bk-2) 30 g / L

Proxel 5g / L

Urea 10g / L

Benzotriazole 3g / L

(Liquid component)

Diethylene glycol monobutyl ether (DGB) 120 g / L

Glycerin (GR) 125 g / L

Diethylene glycol (DEG) 100 g / L

2-pyrrolidone 35g / L

Triethanolamine (TEA) 8 g / L

Surfinol STG (SW) 10g / L

The structure of the said dye is shown below.

Ink sets of these inks were prepared. In addition, the additives described later were added to the yellow ink 101 to prepare yellow inks 102 to 107. Additives (AC-1, 3, 7, 9, 13) are compounds that can chemically interact with the dyes in the ink. The yellow ink thus prepared was separately mixed with other inks to produce another ink set.

These inks were loaded into the ink cartridges of Epson's inkjet printer PM-980C, and the printer was driven to print image patterns of six different colors of C, M, Y, B, G, and R in different levels of gray. Printed.

The award sheet used here is Fuji Photo Film's inkjet paper and photo glossy paper "Gasai".

The image retention of the sample was tested and evaluated.

(1) Light fastness was evaluated as follows: The image density Ci of the fresh sample immediately after printing was measured with a reflectometer (X-Rite 310TR). The printed image is then exposed to xenon light (85,000 lux) for 21 days using a weather tester from Atlas, and then the image concentration Cf is measured. The dye residual ratio is obtained from {(Cf / Ci) × 100}, and is taken as the light fastness of the ink tested. In the dye remaining ratio, three points having yellow reflection concentrations of 1, 1.5, and 2 were measured for all samples. Samples having a dye residual ratio of 80% or more at all points were good (○); Samples having a dye residual ratio of less than 80% at two points were usually (Δ); Samples having a dye residual ratio of less than 80% at all three points were regarded as defective (×).

(2) Ozone resistance was evaluated as follows: Printed samples were stored for 7 days in a box with a constant ozone gas concentration of 5 ppm. Before and after exposure to ozone gas, the image concentration of each sample is measured with a reflectometer (X-Rite 310TR), and the dye residual ratio of each sample is obtained. In the dye residual ratio, three points having yellow reflectivity 1, 1.5 and 2 were measured for all samples. The ozone gas concentration in the box is kept constant using an ozone gas monitor (Applics' Model OZG-EM-01).

The samples tested in this way are divided into three grades: Samples having a dye residual ratio of at least 80% at all points were good (○); Samples having a dye residual ratio of less than 80% at one or two points were usually (Δ); Samples having a dye residual ratio of less than 80% at all three points were regarded as defective (×).

The results obtained are shown in the table below. The control sample is a commercially available ink set of PM-980C.

The effect of this invention becomes clear from the above result.

(Example 2)

Ultrapure water (resistance, 18 MΩ or more) was added to the component described later to be 1 L, followed by stirring for 1 hour while heating to 30 to 40 ° C. The resulting mixture was then filtered under reduced pressure through a micro filter having an average pore size of 0.25 μm. Ink of each color was thus prepared.

[Prescription of Photocyan Ink, LC-201]

(Solid components)

Cyan dye (C-1) 10 g / L

Urea (UR) 15g / L

Benzotriazole (BTZ) 0.08 g / L

Proxel XL2 (PXL) 3.5g / L

(Liquid component)

Triethylene glycol (TEG) 50 g / L

Glycerin (GR) 100 g / L

Triethylene glycol monobutyl ether (TGB) 60 g / L

1,5-pentanediol (PTD) 40 g / L

Isopropanol (IPA) 20 g / L

Triethanolamine (TEA) 7 g / L

Surfinol STG (SW) 10g / L

[Prescription of Cyan Ink, C-201]

(Solid components)

Cyan dye (C-1) 30 g / L

Urea (UR) 40 g / L

Benzotriazole (BTZ) 0.08 g / L

Proxel XL2 (PXL) 3.5g / L

(Liquid component)

Triethylene glycol (TEG) 40 g / L

Glycerin (GR) 100 g / L

Triethylene glycol monobutyl ether (TGB) 70 g / L

1,5-pentanediol (PTD) 50 g / L

Isopropanol (IPA) 20 g / L

Triethanolamine (TEA) 7 g / L

Surfinol STG (SW) 10g / L

[Prescription of Photo Magenta Ink LM-201]

(Solid components)

Magenta Dye (M-1) 7.5g / L

Urea (UR) 10g / L

Proxel 5g / L

(Liquid component)

Triethylene glycol (TEG) 40 g / L

Glycerin (GR) 100 g / L

Triethylene glycol monobutyl ether (TGB) 60 g / L

1,5-pentanediol (PTD) 40 g / L

Isopropanol (IPA) 20 g / L

Triethanolamine (TEA) 6.9 g / L

Surfinol STG (SW) 10g / L

[Magenta Ink, M-201 Prescription]

(Solid components)

Magenta Dye (M-1) 23g / L

Urea (UR) 15g / L

Proxel 5g / L

(Liquid component)

Triethylene glycol (TEG) 50 g / L

Glycerin (GR) 100 g / L

Triethylene glycol monobutyl ether (TGB) 50 g / L

1,5-pentanediol (PTD) 40 g / L

Isopropanol (IPA) 20 g / L

Triethanolamine (TEA) 6.9 g / L

Surfinol STG (SW) 10g / L

[Yellow Ink, Prescription of Y-201]

(Solid components)

Yellow dye (Y-1) 35 g / L

Proxel 3.5g / L

Benzotriazole (BTZ) 0.08 g / L

Urea 10g / L

(Liquid component)

Triethylene glycol (TEG) 40 g / L

Glycerin (GR) 100 g / L

Triethylene glycol monobutyl ether (TGB) 70 g / L

1,5-pentanediol (PTD) 60 g / L

Isopropanol (IPA) 20 g / L

Triethanolamine (TEA) 8 g / L

Surfinol STG (SW) 10g / L

[Prescription of Black Ink, Bk-201]

(Solid components)

75 g / L of black dye (Bk-1)

Black dye (Bk-2) 30 g / L

Proxel 5g / L

Urea 10g / L

Benzotriazole 3g / L

(Liquid component)

Triethylene glycol (TEG) 60 g / L

Glycerin (GR) 100 g / L

Triethylene glycol monobutyl ether (TGB) 70 g / L

1,5-pentanediol (PTD) 60 g / L

Isopropanol (IPA) 20 g / L

Triethanolamine (TEA) 8 g / L

Surfinol STG (SW) 10g / L

Ink sets of these inks were prepared. Moreover, the black ink 202-207 was produced by adding the additive mentioned later to black ink 201. The black ink thus prepared was mixed with other inks separately to prepare other ink sets.

These inks were loaded into the ink cartridges of Canon's inkjet printer PIXUS950i, and the printer was driven to print image patterns of varying density in six levels of C, M, Y, B, G, and R in steps of gray. .

The award sheets used here are copyboard paper, inkjet paper of Fuji Photo Film, and photo-gloss paper "Gasai".

Image fastness was evaluated in the same manner as in Example 1 except for the gray portion of each sample. The image concentration was determined by converting the image concentration into the reflection density (Dvis) of each sample through a visual filter.

The results are shown below.

The above results clearly demonstrate the effect of the first aspect of the present invention.

(Example 3)

Ultrapure water (resistance, 18 MΩ or more) was added to the component described later to be 1 L, followed by stirring for 1 hour while heating to 30 to 40 ° C. The resulting mixture was then filtered under reduced pressure through a micro filter having an average pore size of 0.25 μm. Thus, ink of each color was produced.

[Prescription of Light Cyan Ink]

(Solid components)

Cyan dye (C-1) 20 g / L

Urea (UR) 15g / L

Benzotriazole (BTZ) 0.08 g / L

Proxel XL2 (PXL) 3.5g / L

(Liquid component)

Triethylene glycol (TEG) 110 g / L

Glycerin (GR) 130 g / L

Triethylene glycol monobutyl ether (TGB) 110 g / L

2-pyrrolidone (PRD) 60 g / L

Triethanolamine (TEA) 7 g / L

Surfinol STG (SW) 10g / L

[Prescription of Cyan Ink]

(Solid components)

Cyan Dye (C-1) 60g / L

Urea (UR) 30 g / L

Benzotriazole (BTZ) 0.08 g / L

Proxel XL2 (PXL) 3.5g / L

(Liquid component)

Triethylene glycol (TEG) 110 g / L

Glycerin (GR) 130 g / L

Triethylene glycol monobutyl ether (TGB) 130 g / L

2-pyrrolidone (PRD) 60 g / L

Triethanolamine (TEA) 7 g / L

Surfinol STG (SW) 10g / L

Dye C-1: A / B = 75/25

[Prescription of Light Magenta Ink]

(Solid components)

Magenta Dye (M-1) 7.5g / L

Urea (UR) 10g / L

Proxel 5g / L

(Liquid component)

Diethylene glycol (DEG) 90 g / L

Glycerin (GR) 70 g / L

Triethylene glycol monobutyl ether (TGB) 70 g / L

Triethanolamine (TEA) 6.9 g / L

Surfinol STG (SW) 10g / L

[Prescription of Magenta Ink]

(Solid components)

Magenta Dye (M-1) 23g / L

Urea (UR) 15g / L

Proxel 5g / L

(Liquid component)

Diethylene glycol (DEG) 90 g / L

Glycerin (GR) 70 g / L

Triethylene glycol monobutyl ether (TGB) 70 g / L

Triethanolamine (TEA) 6.9 g / L

Surfinol STG (SW) 10g / L

[Prescription of Yellow Ink]

(Solid components)

Yellow dye (Y-1) 35 g / L

Proxel XL2 (PXL) 3.5g / L

Benzotriazole (BTZ) 0.08 g / L

Urea (UR) 10g / L

(Liquid component)

Triethylene glycol monobutyl ether (TEG) 130 g / L

Glycerin (GR) 115 g / L

Diethylene glycol (DEG) 120 g / L

2-pyrrolidone 35g / L

Triethanolamine (TEA) 8 g / L

Surfinol STG (SW) 10g / L

[Prescription of Black Ink]

(Solid components)

75 g / L of black dye (Bk-1)

Yellow dye (Y-2) 30 g / L

Proxel XL2 (PXL) 5g / L

Urea (UR) 10g / L

Benzotriazole (BZT) 3 g / L

(Liquid component)

Diethylene glycol monobutyl ether (DGB) 120 g / L

Glycerin (GR) 105 g / L

Diethylene glycol (DEG) 100 g / L

2-pyrrolidone (PRD) 35 g / L

Triethanolamine (TEA) 8 g / L

Surfinol STG (SW) 10g / L

Ink sets of these inks were prepared. This is IS-101.

The oxidation potential of the yellow dye (Y-1) is 1.22 V, lambda max is 445 nm, and the absorbance ratio I (λ max +70 nm) / I (λ max) is 0.17.

Other ink sets IS-102 to IS-105 were prepared as in the ink set IS-101, but the solvent amounts in the yellow ink and the black ink were changed as shown in Table 18 below.

These inks were loaded into the ink cartridges of the Epson inkjet printer PM-980C. The printer was set to a six-color print mode and driven to print an image pattern on the award sheet in which the density of the C, M, Y, B, G, and R colors was changed in steps of six colors and gray. The award sheet used here is Fuji Photo Film's inkjet paper and photo glossy paper "Gasai".

The printed image was tested and evaluated by the method described below.

Light fastness was evaluated as follows: Image density of fresh samples immediately after printing was measured by X-Rite 310TR. The printed image is exposed to xenon ore (85,000 lux) for 20 days using an Atlas weather tester, and then visually observed.

Ozone resistance was evaluated as follows: Printed samples were stored in a box with a constant ozone gas concentration of 5 ppm for 96 hours, and then visually inspected for burns.

In the two tests for the image fastness, a sample having a naturally discolored color with good color balance in the gray gradation region was good (○); Gray gradations were not balanced and samples with discontinuous color change were regarded as defective (×).

The results are shown in Table 19 below. The control sample is a commercially available ink set of PM-980C.

From the results in Table 19, the ink set of the present invention having a low water-soluble organic solvent concentration for the yellow ink than that for the black ink, or a lower total solvent concentration for the yellow ink than for the black ink has excellent weather resistance. It can be confirmed that good color balance can be maintained even after giving a good image and fading, and clearly demonstrates the effect of the present invention.

(Example 4)

Ultrapure water (resistance, 18 MΩ or more) was added to the component described later to be 1 L, followed by stirring for 1 hour while heating to 30 to 40 ° C. The resulting mixture was then filtered under reduced pressure through a micro filter having an average pore size of 0.25 μm. Ink of each color was thus prepared.

[Prescription of Photocyan Ink]

(Solid components)

Cyan dye (C-1) 10 g / L

Urea (UR) 15g / L

Benzotriazole (BTZ) 0.08 g / L

Proxel XL2 (PXL) 3.5g / L

(Liquid component)

Triethylene glycol (TEG) 50 g / L

Glycerin (GR) 100 g / L

Triethylene glycol monobutyl ether (TGB) 60 g / L

1,5-pentanediol (PTD) 40 g / L

Isopropanol (IPA) 20 g / L

Triethanolamine (TEA) 7 g / L

Surfinol STG (SW) 10g / L

[Prescription of Cyan Ink]

(Solid components)

Cyan dye (C-1) 30 g / L

Urea (UR) 40 g / L

Benzotriazole (BTZ) 0.08 g / L

Proxel XL2 (PXL) 3.5g / L

(Liquid component)

Triethylene glycol (TEG) 40 g / L

Glycerin (GR) 100 g / L

Triethylene glycol monobutyl ether (TGB) 70 g / L

1,5-pentanediol (PTD) 50 g / L

Isopropanol (IPA) 20 g / L

Triethanolamine (TEA) 7 g / L

Surfinol STG (SW) 10g / L

[Prescription of Photo Magenta Ink]

(Solid components)

Magenta Dye (M-1) 7.5g / L

Urea (UR) 10g / L

Proxel XL2 (PXL) 5g / L

(Liquid component)

Triethylene glycol (TEG) 40 g / L

Glycerin (GR) 100 g / L

Triethylene glycol monobutyl ether (TGB) 60 g / L

1,5-pentanediol (PTD) 40 g / L

Isopropanol (IPA) 20 g / L

Triethanolamine (TEA) 6.9 g / L

Surfinol STG (SW) 10g / L

[Prescription of Magenta Ink]

(Solid components)

Magenta Dye (M-1) 23g / L

Urea (UR) 15g / L

Proxel XL2 (PXL) 5g / L

(Liquid component)

Triethylene glycol (TEG) 50 g / L

Glycerin (GR) 100 g / L

Triethylene glycol monobutyl ether (TGB) 50 g / L

1,5-pentanediol (PTD) 40 g / L

Isopropanol (IPA) 20 g / L

Triethanolamine (TEA) 6.9 g / L

Surfinol STG (SW) 10g / L

[Prescription of Yellow Ink]

(Solid components)

Yellow dye (Y-1) 35 g / L

Proxel XL2 (PXL) 3.5g / L

Benzotriazole (BTZ) 0.08 g / L

Urea 10g / L

(Liquid component)

Triethylene glycol (TEG) 80 g / L

Glycerin (GR) 120 g / L

Triethylene glycol monobutyl ether (TGB) 70 g / L

1,5-pentanediol (PTD) 60 g / L

Isopropanol (IPA) 20 g / L

Triethanolamine (TEA) 8 g / L

Surfinol STG (SW) 10g / L

[Prescription of Black Ink]

(Solid components)

75 g / L of black dye (Bk-1)

Yellow dye (Y-1) 30 g / L

Proxel XL2 (PXL) 5g / L

Urea 10g / L

Benzotriazole (BTZ) 3 g / L

(Liquid component)

Triethylene glycol (TEG) 60 g / L

Glycerin (GR) 100 g / L

Triethylene glycol monobutyl ether (TGB) 70 g / L

1,5-pentanediol (PTD) 50 g / L

Isopropanol (IPA) 20 g / L

Triethanolamine (TEA) 8 g / L

Surfinol STG (SW) 10g / L

Ink sets of these inks were prepared. This is IS-201.

The other ink sets IS-202 to IS-205 were manufactured as in the ink set IS-201, but the amount of solvent in the yellow ink and the black ink was changed as shown in Table 20 below.

These inks were loaded into ink cartridges of Canon's inkjet printer PIXUS950i. The printer was set to a six-color print mode and driven to print an image pattern on the award sheet in which the density of the C, M, Y, B, G, and R colors was changed in steps of six colors and gray. The award sheet used here is Fuji Photo Film's inkjet paper and photo glossy paper "Gasai".

The printed image was tested and evaluated in the same manner as in Example 1. The results are shown in Table 21 below. The control sample is a commercial ink set from PIXUS950i.

From the results in Table 21, the ink set of the present invention having a low water-soluble organic solvent concentration for the yellow ink than that for the black ink, or a lower total solvent concentration for the yellow ink than for the black ink has excellent weather resistance. It can be seen that good color balance can be maintained even after imparting a good image and fading, and clearly demonstrates the effect of the present invention.

(Example 5)

After adding deionized water so that it might become 1L to the component mentioned later, it stirred for 1 hour, heating at 30-40 degreeC. Then, KOH (10 mol / L) was added to the resulting mixture, and adjusted to have a pH of 9, and then filtered under reduced pressure through a micro filter having an average pore size of 0.25 μm. Thus, yellow ink was produced.

Yellow dye (A-3) 65 g / L

Diethylene Glycol 85g / L

Glycerin 154g / L

Triethylene glycol monobutyl ether 130 g / L

Triethanolamine 1 g / L

Benzotriazole 0.03 g / L

Proxel XL2 3g / L

Surfactant (W-1) 10 g / L

The dyes and additives were varied to produce other inks, light magenta inks, magenta inks, light cyan inks, cyan inks, dark yellow inks and black inks, as in Inkset 101.

W-2 (Compound X1-3)

W-3 (Compound X2-3)

Like Ink Set 101, other Ink Sets 102-106 were prepared, but the surfactants, water miscible high boiling point organic solvents and dyes were changed as shown in Table 23 below.

These ink sets 101-106 were loaded into ink cartridges of Epson's inkjet printer PM-920C, images were printed on ink jet paper and photo glossy paper "Gasai" of Fuji Photo Film, and evaluated by the method described below.

(1) Printability was evaluated as follows: The cartridge was mounted in the printer and ink ejection was confirmed from all the nozzles. Then, all nozzle caps are kept open for three days, and the nozzle check pattern is repeatedly printed. The number of cleanings required for stable ink ejection was counted, and this was regarded as printability retained by the ink set tested.

(2) Image stability (light fastness) was evaluated as follows: A sample printed with a yellow solid image was prepared. The image density Ci of the fresh sample immediately after printing was measured by X-Rite 310. The printed image was then exposed to xenon light (85,000 lux) for 7 days using an Atlas weather tester, and the image concentration Cf was measured. The dye residual ratio was obtained from {(Cf / Ci) × 100} and was taken as the light fastness of the ink tested. In the dye residual ratio, three points having reflectance concentrations of 1, 1.5 and 2 were measured for all samples. Samples having a dye residual of at least 85% at all points were good (A); Samples with a dye residual of less than 85% at two points were usually (B); Samples having a dye residual ratio of less than 85% at all three points were designated as defective (C).

(3) Ozone resistance was evaluated as follows: Printed samples were stored for 3 days in a box having a constant ozone gas concentration of 5 ppm. Before and after exposure to ozone gas, the image concentration of each sample was measured with a reflectometer (X-Rite 310TR), and the dye residual ratios of all the samples were determined. In the dye remaining ratio, three points having original image concentrations of 1, 1.5, and 2 were measured for all samples. Samples having a dye residual of at least 80% at all points were good (A); Samples having a dye residual of less than 85% at one or two points were usually (B); Samples having a dye residual ratio of less than 70% at all three points were designated as defective (C).

(4) Temperature fluctuation tolerance was evaluated as follows: An image having a reflection concentration of 1.5 at the maximum lambda max was printed, and the initial concentration Da of the image was obtained. Immediately after printing, the sample was left to stand at 80 ° C. and 15% RH for 7 days, and the concentration Db was obtained. The concentration change is represented by the following formula.

Change in concentration (%) = (Db-Da) / Da × 100

Table 30 shows the results of (1) to (4).

Table 24 shows that the ink composition of the present invention ensures good inkjet stability and image fastness.

The same results as above were obtained even when the award site was changed to Epson PM Photo Paper PM and Canon PR101.

Example 6

The same ink as in Example 5 was attached to the ink cartridge of Canon's inkjet printer BJ-F850, and images were printed on ink jet paper and photo glossy paper "EX" of Fuji Photo Film, and evaluated in the same manner as in Example 5. Also in this case, the same result as in Example 5 was obtained. The same result was obtained also when the award site was changed to Epson PM Photo Paper PM and Canon PR101.

According to a first aspect of the present invention, the present invention provides an ink containing at least one dye having a heterocyclic structure and at least one compound capable of chemically interacting with the dye and having good color and image fastness; An ink jet ink set containing the ink; And it provides an inkjet recording method comprising the step of using any of these.

According to a second aspect of the present invention, the present invention provides an ink set for imparting an image having good color balance even after good weather resistance and fading.

According to the third aspect of the present invention, the present invention provides an aqueous ink set which is advantageous in terms of handling, odorless and safety, and which can secure a recording image excellent in weatherability due to good discharge stability.

Claims (23)

Dyes; An ink containing water and / or a water miscible organic solvent, And the dye contains a dye compound having at least one heterocyclic structure, and the ink contains at least one compound which can chemically interact with the dye compound as an additive. The ink according to claim 1, wherein the dye compound has two aromatic heterocycles bonded to each other through an azo bond. The ink according to claim 1, wherein the dye compound has a metal chelated aromatic heterocyclic structure. The ink according to any one of claims 1 to 3, wherein the additive is a hydrogen bonding compound. The method according to any one of claims 1 to 4, wherein the additive is a mixture of a dye having a heterocyclic structure in a molar ratio of 1: 1 and has a maximum concentration of 1 mmol / L in a visible absorption spectrum of a diluted aqueous solution. [lambda] max is shifted by 5 nm or more compared with the case where the said additive is not contained. The ink according to any one of claims 1 to 5, wherein the additive has a cyclic amide structure, and the dye compound has a six-membered aromatic heterocycle containing nitrogen. The ink according to any one of claims 1 to 6, wherein the additive is a compound having a partial structure represented by the following general formula (A).

Wherein X represents an oxygen atom, a sulfur atom or NR (R represents a hydrogen atom or an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group); Z represents a 5-8 membered ring. Atom groups to form are shown.) An ink set comprising at least one ink according to any one of claims 1 to 7. An inkjet recording method comprising recording an image with an inkjet printer using one of the ink or ink set according to any one of claims 1 to 8. At least one yellow ink containing an aqueous medium and a yellow dye dispersed or dissolved in the aqueous medium; And a black ink containing at least one yellow dye, wherein the dye has an oxidation potential of more than 1.0 V (vs SCE); λ max is in the range of 390 nm to 470 nm; An ink set, wherein the absorbance ratio I (λ max +70 nm) / I (λ max) is at most 0.4, wherein I (λ max) is an absorbance of λ max, and I (λ max +70 nm) is an absorbance of λ max +70 nm. The ink set according to claim 10, wherein the absorbance ratio I (λ max + 70 nm) / I (λ max) of the yellow dye is 0.2 at most. The ink set according to claim 10 or 11, wherein the yellow dye is a compound represented by the following general formula (1). (A-N = N-B) n-L (1) (Wherein A and B each independently represent a heterocyclic group which is substituted as necessary; n is 1 or 2; L represents a hydrogen atom or a substituent bonded to any predetermined position of A or B.) The method according to any one of claims 10 to 12, wherein the accelerated fading rate constant of the yellow ink is smaller than that of the black ink, and the accelerated fading rate constant is the following method: printing the ink to be analyzed on the reflection medium, and The reflection concentration D _B is measured with a status A filter; In the yellow region, one point of the sample having a reflection density (D _B ) of 0.90 to 1.10 is defined as the initial concentration of the ink, and the printed sample is forcibly faded by using an ozone fading tester that always generates 5 ppm of ozone. ; An ink set, characterized in that it is determined by a method of measuring the time at which the reflection density of the discolored sample is reduced to 80% of the initial concentration of the original sample, and inducing the accelerated fading rate constant of the ink therefrom. The ink set according to any one of claims 10 to 13, wherein the concentration of the water-soluble organic solvent in the yellow ink is lower than in the black ink. The total concentration of the solvent in the yellow ink is lower than that of the black ink, and the total concentration of the solvent is a glycol organic solvent, a glycol alkyl ether organic solvent, and an amide organic solvent. Ink set, characterized in that determined by summing the concentration of any two or more solvents selected from the solvent. An inkjet color recording method comprising recording an image on an aqueous material having an aqueous layer on a support using an ink composition containing at least one of a yellow azo dye and a black azo dye, and a water miscible organic solvent. And the absolute value of the image concentration change at the point where the reflection density in the? Max region of the image is 1.5 is at most 20%. 17. The image of claim 16, wherein an image having a reflectance concentration of 1.5 in the lambda max region is printed, and the change in density is represented by the following general formula (wherein Da represents the initial concentration of the image region, and Db is 80 DEG C and 15% RH atmosphere) Indicative of the density after being left for 7 days). Change in concentration (%) = (Db-Da) / Da × 100 18. The inkjet color recording method according to claim 16 or 17, wherein the dye is a yellow dye represented by the following general formula (1). (A-N = N-B) n-L (1) (Wherein A and B each independently represent a heterocyclic group which is substituted as necessary; L represents a hydrogen atom, a chemical bond or a divalent linking group; n is 1 or 2; provided that when n is 1, L is Is a hydrogen atom, A and B are both monovalent heterocyclic groups, when n is 2, L is a chemical bond or a divalent linking group, one of A and B is a monovalent heterocyclic group, and the other is a divalent heterocyclic group. Ventilation; when n is 2, the two A's may be the same or different, and the two B's may be the same or different). 19. The inkjet color recording method according to any one of claims 16 to 18, wherein the ink composition further contains a surfactant, and the surfactant is a betaine-based surfactant. 20. The inkjet color recording method according to claim 19, wherein the betaine-based surfactant is represented by the following general formula (6). (R) p-N- [L- (COOM) q] r (6) Wherein R represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; L represents a divalent linking group; M represents a hydrogen atom, an alkali metal atom, an ammonium group, a protonated organic amine or a nitrogen-containing heterocyclic group, or a quaternary An ammonium ion group, which is a group which does not exist as a cation when it is a counter ion to an ammonium ion having an N atom in the formula; q represents an integer of 1 or more; r represents an integer of 1 to 4; An integer of 0 to 4; p + r is 3 or 4; when p + r is 4, the N atom in the formula is a protonated ammonium atom (= N ⁺ =); when q is 2 or more, COOM May be the same or different; when r is 2 or more, (L- (COOM) q) may be the same or different; when p is 2 or more, R may be the same or different.) The ink composition according to any one of claims 16 to 20, wherein the ink composition is one or more of triethylene glycol monobutyl ether, diethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, and dipropylene glycol monomethyl ether. And a water-miscible organic solvent. 22. The inkjet color recording method according to any one of claims 16 to 21, wherein the dye has an oxidation potential that is greater than 1.0 V (vs SCE). 23. The inkjet color recording method according to any one of claims 16 to 22, wherein the aqueous layer contains inorganic pigment particles of white color.